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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 19 records

Al 2 O 3 /TiO 2 coated separators: Roll-to-roll processing and implications for improved battery safety and performance

Heat generation is one of the major concerns with lithium-ion batteries (LIB) while charging them at higher currents, which could inadvertently impact the rate performance and reduce the safety of the cell. Polymer separator is one of the least thermal conductive components of a LIB. In addition, commercial separators for LIB are made from polyolefin membranes that tend to shrink and curl at higher temperatures due to their lower melting temperature (~130 °C). Developing separators with improved thermal stability and higher electrolyte uptake is essential for enhancing the safety as well as the performance of the LIB. In this work, a thin layer of ceramic coatings (Al 2 O 3 and TiO 2 ) is applied on propylene (PP) membrane to improve the thermal stability and electrolyte affinity without compromising the rate performance. A slurry with 100% Al 2 O 3 coated on the polypropylene separator exhibited the best improvement in thermal stability ( shrinkage of 0.6% vs 6.0% for uncoated membrane) and excellent rate performance with 92% capacity retention at 2C. The Al 2 O 3 coated separator demonstrated excellent electrolyte wettability compared to the uncoated membrane. The cross-plane thermal conductivity of the ceramic coated separators is analyzed to understand their heat transfer behavior. The thermal conductivity of the separator is improved by ~3.2 times with the Al 2 O 3 coating.

25 ENERGY STORAGE↗

Ceramic composite liner material for gas turbine combustors

Advanced commercial and military gas turbine engines may operate at combustor outlet temperatures in excess of 1920 K (3000 F). At these temperatures combustors liners experience extreme convective and radiative heat fluxes. The ability of a plasma sprayed ceramic coating to reduce liner metal temperature has been recognized. However, the brittleness of the ceramic layer and the difference in thermal expansion with the metal substrate has caused cracking, spalling and some separation of the ceramic coating. Research directed at turbine tip seals (or shrouds) has shown the advantage of applying the ceramic to a compliant metal pad. This paper discusses recent studies of applying ceramics to combustor liners in which yttria stabilized zirconia plasma sprayed on compliant metal substrates which were exposed to near stoichiometric combustion, presents performance and durability results, and describes a conceptual design for an advanced, small gas turbine combustor. Test specimens were convectively cooled or convective-transpiration cooled and were evaluated in a 10 cm square flame tube combustor at inlet air temperatures of 533 K (500 F) and at a pressure of 0.5 MPa (75 psia). The ceramics were exposed to flame temperatures in excess of 2000 K (3320 F). Results appear very promising with all 30 specimens surviving a screening test and one of two specimens surviving a cyclic durability test.

Ercegovic, D. B.↗

Modeling of Thermal Barrier Coatings

The project examined the effectiveness of studying the creep behavior of thermal barrier coating system through the use of a general purpose, large strain finite element program, NIKE2D. Constitutive models implemented in this code were applied to simulate thermal-elastic and creep behavior. Four separate ceramic-bond coat interface geometries were examined in combination with a variety of constitutive models and material properties. The reason for focusing attention on the ceramic-bond coat interface is that prior studies have shown that cracking occurs in the ceramic near interface features which act as stress concentration points. The model conditions examined include: (1) two bond coat coefficient of thermal expansion curves; (2) the creep coefficient and creep exponent of the bond coat for steady state creep; (3) the interface geometry; and (4) the material model employed to represent the bond coat, ceramic, and superalloy base.

Ferguson, B. L.↗

Effect of Environmental Exposures on Fatigue Life of P/M Disk Superalloys

As the temperature capability of Ni-base superalloy powder metallurgy disks is steadily increased, environmental resistance and protection of advanced nickel-based turbine disk components are becoming increasingly important. Localized surface hot corrosion attack and damage from oxidation have been shown to impair disk fatigue life and may eventually limit disk operating temperatures. NASA Research Announcement (NRA) contracts have been awarded to GE Aviation and Honeywell Aerospace to separately develop fatigue resistant metallic and ceramic coatings for corrosion resistance and the corrosion/fatigue results of selected coatings will be presented. The microstructural response of a bare ME3 disk superalloy has been evaluated for moderate (704 C) and aggressive (760-816 C) oxidizing exposures up to 2,020 hours. Cross section analysis reveals sub-surface damage (significant for aggressive exposures) that consists of Al2O3 "fingers", interfacial voids, a recrystallized precipitate-free layer and GB carbide dissolution. The effects of a Nichrome corrosion coating on this microstructural response will also be presented.

Draper, Susan↗

Machined electrostatic sector for mass spectrometer

An electrostatic sector device for a mass spectrometer is formed from a single piece of machinable ceramic. The machined ceramic is coated with a nickel coating, and a notch is etched in the nickel coating to form two separated portions. The sector can be covered by a cover formed from a separate piece of machined ceramic.

Sinha, Mahadeva P.↗

Residual Stresses Modeled in Thermal Barrier Coatings

Thermal barrier coating (TBC) applications continue to increase as the need for greater engine efficiency in aircraft and land-based gas turbines increases. However, durability and reliability issues limit the benefits that can be derived from TBC's. A thorough understanding of the mechanisms that cause TBC failure is a key to increasing, as well as predicting, TBC durability. Oxidation of the bond coat has been repeatedly identified as one of the major factors affecting the durability of the ceramic top coat during service. However, the mechanisms by which oxidation facilitates TBC failure are poorly understood and require further characterization. In addition, researchers have suspected that other bond coat and top coat factors might influence TBC thermal fatigue life, both separately and through interactions with the mechanism of oxidation. These other factors include the bond coat coefficient of thermal expansion, the bond coat roughness, and the creep behavior of both the ceramic and bond coat layers. Although it is difficult to design an experiment to examine these factors unambiguously, it is possible to design a computer modeling "experiment" to examine the action and interaction of these factors, as well as to determine failure drivers for TBC's. Previous computer models have examined some of these factors separately to determine their effect on coating residual stresses, but none have examined all the factors concurrently. The purpose of this research, which was performed at DCT, Inc., in contract with the NASA Lewis Research Center, was to develop an inclusive finite element model to characterize the effects of oxidation on the residual stresses within the TBC system during thermal cycling as well as to examine the interaction of oxidation with the other factors affecting TBC life. The plasma sprayed, two-layer thermal barrier coating that was modeled incorporated a superalloy substrate, a NiCrAlY bond coat, and a ZrO2-8 wt % Y2O3 ceramic top coat. We examined the effect on stress during burner rig thermal cycling of the following independent variables: creep in the bond coat and top coat, oxidation, bond coat coefficient of thermal expansion, number of thermal cycles, and interfacial roughness. All these factors were suspected of influencing TBC failure. The model showed that all the material properties studied had a significant effect on the coating's residual stresses if the interface of the bond coat was rough. Bond coat expansion, bond coat oxidation, and bond coat creep had the highest effect on coating stresses, and these were highly interactive. The model also showed that the mechanism of stress generation during thermal cycling changed with the number of thermal cycles. Bond coat and top coat creep dominated stress generation during early thermal cycles, greatly increasing delamination stresses at the peaks of the bond coat. Therefore, creep is the prime driver for delamination cracking early in life, but cracking is limited to the bond coat peak region. Oxidation of the bond coat, on the other hand, tended to dominate stress generation during later cycles by greatly increasing delamination stresses over bond coat valleys. These results indicate that oxidation is the driver for the continued cracking necessary to cause ceramic layer spallation.

Freborg, A. M.↗

Lithium battery

The present disclosure describes various types of batteries, including lithium-ion batteries having an anode assembly comprising: an anode comprising a first porous ceramic matrix having pores; and a ceramic separator layer affixed directly or indirectly to the anode; a cathode; an anode-side current collector contacting the anode; and anode active material comprising lithium located within the pores or cathode active material located within the cathode; wherein, the ceramic separator layer is located between the anode and the cathode, no electrically conductive coating on the pores contacts the separator layer, and in a fully charged state, lithium active material in the anode does not contact the separator layer. Also disclosed are methods of making and methods of using such batteries.

25 ENERGY STORAGE↗

On electrolyte wetting through lithium-ion battery separators

The wettability by electrolyte is a critical characteristic of lithium-ion battery separators since electrolyte absorption is essential for ionic transport. Most importantly, fast absorption of electrolyte facilitates the electrolyte filling and wetting processes during the battery assembly. However, theoretical or experimental investigation of separator wettability has rarely been reported, and thus very little quantitative data can be found in the existing literature. Here, innovative experimental techniques and associated analytical models have been developed to fully characterize the electrolyte wetting behavior through battery separators. Both in-plane and through-plane imbibition processes are investigated. The results show that, electrolyte needs significantly longer time to wet separators than it does for commercial electrodes. The wetting rate depends significantly on the pore size, porosity, and micro-structure of the separators. Electrolyte in-plane wetting is only observed in the separators manufactured by the wet process. Increasing separator porosity and pore size is shown to be substantially increasing through-plane wetting rate. In addition, ceramic coating is shown to increase in-plane wetting but retard through-plane wetting.

25 ENERGY STORAGE↗

Highly Loaded Sulfur Cathode, Coated Separator and Gel Electrolyte for High Rate Li-Sulfur Batteries

As one of DOE Battery 500 Seedling projects, Cornell University and EIC Labs investigated and developed i) highly loaded sulfur cathodes (> 3 mg/cm 2 ), ii) hybrid separators, and iii) gel ceramic electrolytes (GCE) to mitigate the low rate capability, shuttling effect and limited cycle life in high performance Li-Sulfur batteries. Scalable nanomanufacturing processes such as air-controlled electrospray (ACES) and gas-assisted electrospinning (GAES) have been utilized to develop directly deposited electrodes and polymer/ceramic hybrid separators. First, in the development of highly loaded cathodes, alternating layers of sulfur impregnated mesoporous carbon and graphene were fabricated via ACES and the resulting layered cathodes and coated separators exhibit higher capacity and capacity retention (about 1,000 mAh/g capacity with less than 0.02% fade/cycles) than single layer cathode or cathode prepared by conventional slurry cast. Alternating layer approach via ACES has been applied to high loading systems (3 - 5 mg S/cm 2 ), demonstrating the potential to increase sulfur utilization and capacity retention. We have also incorporated iron oxides (Fe 3 O 4 ) into S/mesoporous carbon/graphene cathodes to enhance sulfur utilization and mitigation of polysulfide shuttling. and the effect of Fe 3 O 4 in mesoporous carbon and Gr is highly pronounced at high C rates of 1C and 2C cycling performance. To further improve the cathodes at high rates, graphene nanoribbons (GNR) which can promote ion transport were incorporated in the cathode, resulting in 550 mAh/g at 5C/5C rates. Hybrid Li-ion/Li-S cathodes has also been explored to better engage unreacted polysulfides during charge/discharge. S/LFP hybrid cathodes offer higher sulfur utilization and enhanced rate capability, as well as higher areal loading. This study suggests inclusion of iron phosphide (Fe2P) which can chemically interact with polysulfides can further enhance sulfur utilization and mitigation of soluble polysulfides at high rates. Secondly, in the development of hybrid separators, we first employed graphene coating on the commercial polyolefin separators, which exhibits higher capability, better capacity retention and enhanced rate capability. To improve the rate capability with enhanced safety features such as thermal stability and nonflammability, we developed polymer/ceramic hybrids based on thermally stable polyimide (PI) and room temperature curable ceramic precursors such as organopolysilazane (OPSZ) or polysilsesquioxanes (PSSQ), which exhibit no shrinkages up to 300 ºC and non-flammability. To improve mechanical properties and electrochemical stability, polybenzimidazole (PBI) and alumina have been incorporated in polymer/ceramic hybrid separator, replacing PI and OPSZ/PSSQ, respectively. Finally, the gel ceramic electrolyte (GCE) based on ceramic cross linkers have been applied to make Li-S cells even safer and also to mitigate the polysulfide shuttling further. The resulting gel ceramic electrolyte offers improved capacity retention and rate capability, and also effectively mitigates polysulfide shuttling which was also confirmed by modeling. Inclusion of high ion conducting additives into GCE together with polymer/ceramic hybrid separators exhibit the higher ionic conductivity than liquid electrolyte with commercial polyolefin separator. We demonstrated that the developed highly loaded sulfur cathodes, polymer/ceramic hybrid separators and gel ceramic electrolyte can effectively mitigate the low rate capability, shuttling effect and limited cycle life in high performance Li-Sulfur batteries with improved safety.

25 ENERGY STORAGE↗

Sodium electrochemical interfaces with NaSICON-type ceramics

The present invention is directed to the modification of sodium electrochemical interfaces to improve performance of NaSICON-type ceramics in a variety of electrochemical applications. Enhanced mating of the separator-sodium interface by means of engineered coatings or other surface modifications results in lower interfacial resistance and higher performance at increased current densities, enabling the effective operation of molten sodium batteries and other electrochemical technologies at low and high temperatures.

36 MATERIALS SCIENCE↗

Local electrical degradations of solid-state electrolyte by nm-scale operando imaging of ionic and electronic transports

We report on degradation mechanisms of solid-state electrolyte (SSE) based on insights from nm-scale ionic conduction and electronic leakage for solid-state batteries. The significantly different local degradations revealed by nm-scale ionic and electronic transport imaging demonstrate the need for this nm-scale investigation. State-of-the-art lithium-ion conductive glass ceramic (Li 2 O–Al 2 O 3 –SiO 2 –P 2 O5–TiO2-GeO2) SSE shows at least two types of degradations spatially separated within the SSE, namely: (1) ionic conduction blocking and slight electronic leaking and (2) highly electronic shunting. Degradation was significantly suppressed by application of a Li-containing polyacrylonitrile thin coating on both sides of the ceramic SSE. With this coating, the ionic conduction was not reduced by the extensive cycling; instead, it improved slightly, although accompanied by a slight increase in electronic leaking. Our nm-scale transport imaging was achieved using an atomic force microscopy (AFM)-based half-cell setup and a logarithmic-scale amplifier with current sensitivity down to the fA (10-15 A) range. This half-cell setup consisting of an AFM-probe/SSE/Li structure can distinguish the ionic from the electronic current by flipping the bias-voltage polarity. This nm-scale operando imaging opens up novel characterization of ionic and electronic transport in the field of solid-state batteries.

42 ENGINEERING↗

Adhesion, friction and micromechanical properties of ceramics

The adhesion, friction, and micromechanical properties of ceramics, both in monolithic and coating form, are reviewed. Ceramics are examined in contact with themselves, other harder materials, and metals. For the simplicity of discussion, the tribological properties of concern in the processes are separated into two parts. The first part discusses the pull-off force (adhesion) and the shear force required to break the interfacial junctions between contacting surfaces. The role of chemical bonding in adhesion and friction, and the effects of surface contaminant films and temperature on tribological response with respect to adhesion and friction are discussed. The second part deals with abrasion of ceramics. Elastic, plastic, and fracture behavior of ceramics in solid state contact is discussed. The scratch technique of determining the critical load needed to fracture interfacial adhesive bonds of ceramic deposited on substrates is also addressed.

Miyoshi, Kazuhisa↗

Adhesion, friction and micromechanical properties of ceramics

The adhesion, friction, and micromechanical properties of ceramics, both in monolithic and coating form, are reviewed. Ceramics are examined in contact with themselves, other harder materials, and metals. For the simplicity of discussion, the tribological properties of concern in the processes are separated into two parts. The first part discusses the pull-off force (adhesion) and the shear force required to break the interfacial junctions between contacting surfaces. The role of chemical bonding in adhesion and friction, and the effects of surface contaminant films and temperature on tribological response with respect to adhesion and friction are discussed. The second part deals with abrasion of ceramics. Elastic, plastic, and fracture behavior of ceramics in solid state contact is discussed. The scratch technique of determining the critical load needed to fracture interfacial adhesive bonds of ceramic deposited on substrates is also addressed.

Miyoshi, Kazuhisa↗

Electrochemical device comprising thin porous metal sheet

Electrochemical device using thin micro-porous metal sheets. The porous metal sheet may have a thickness less than 200 μm, provides three-dimensional networked pore structures of pore sizes in the range of 2.0 nm to 5.0 μm, and is electrically conductive. The micro-porous metal sheet is used for positively and/or negatively-charged electrodes by providing large specific contact surface area of reactants/electron. Nano-sized catalyst or features can be added inside pores of the porous metal sheet of pore sizes at sub- and micrometer scale to enhance the reaction activity and capacity. Micro-porous ceramic materials may be coated on the porous metal sheet at a thickness of less than 40 μm to enhance the functionality of the porous metal sheet and may function as a membrane separator. The electrochemical device may be used for decomposing molecules and for synthesis of molecules such as synthesis of ammonia from water and nitrogen molecules.

Liu, Wei↗

Protective Coatings for Mitigating Lunar Dust Abrasion and Adhesion

Materials resistant to the harsh lunar environment are needed to support long duration, sustainable missions on the Moon’s surface. Lunar dust poses a significant threat to the durability of components and vehicles due to its fine, jagged morphology and highly abrasive nature. These characteristics result in particles eroding, adhering and/or embedding onto component surfaces and into device confined geometries (e.g., gear housing, interlocking systems, etc.) potentially leading to premature failure. The aim of this work is to identify and characterize wear-resistant materials, including advanced ceramics, for use as protective coatings to minimize abrasion and adhesion caused by lunar dust. Results from testing and evaluation methods devised to elucidate and mimic aspects of lunar dust degradation, including adhesion, abrasion and erosion, as well as the lunar environment, will be presented. Discussion on balancing the need for dust management and tolerance versus dust adhesion mitigation will be shared in context of relevant lunar applications within the NASA Lunar Occupancy Dust Surface Separation Technologies effort, which is part of a NASA-wide effort to enable a sustained lunar presence through the Lunar Surface Innovation Initiative.

lunar dust mitigation↗

Materials and structural aspects of advanced gas-turbine helicopter engines

Advances in materials, coatings, turbine cooling technology, structural and design concepts, and component-life prediction of helicopter gas-turbine-engine components are presented. Stationary parts including the inlet particle separator, the front frame, rotor tip seals, vanes and combustors and rotating components - compressor blades, disks, and turbine blades - are discussed. Advanced composite materials are considered for the front frame and compressor blades, prealloyed powder superalloys will increase strength and reduce costs of disks, the oxide dispersion strengthened alloys will have 100C higher use temperature in combustors and vanes than conventional superalloys, ceramics will provide the highest use temperature of 1400C for stator vanes and 1370C for turbine blades, and directionally solidified eutectics will afford up to 50C temperature advantage at turbine blade operating conditions. Coatings for surface protection at higher surface temperatures and design trends in turbine cooling technology are discussed. New analytical methods of life prediction such as strain gage partitioning for high temperature prediction, fatigue life, computerized prediction of oxidation resistance, and advanced techniques for estimating coating life are described.

Freche, J. C.↗

Chemical Stability of the Fiber Coating/Matrix Interface in Silicon-Based Ceramic Matrix Composites

Carbon and boron nitride are used as fiber coatings in silicon-based composites. In order to assess the long-term stability of these materials, reactions of carbon/Si3N4 and BN/SiC were studied at high temperatures with Knudsen effusion, coupon tests, and microstructural examination. In the carbon/Si3N4 system, carbon reacted with Si3N4 to form gaseous N2 and SiC. The formation of SiC limited further reaction by physically separating the carbon and Si3N4. Consequently, the development of high p(N2) at the interface, predicted from thermochemical calculations, did not occur, thus limiting the potential deleterious effects of the reaction on the composite. Strong indications of a reaction between BN and SiC were shown by TEM and SIMS analysis of the BN/SiC interface. In long-term exposures, this reaction can lead to a depletion of a BN coating and/or an unfavorable change of the interfacial properties, limiting the beneficial effects of the coating.

Lee, Kang N.↗