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NASA NTRS2006

Low conductivity and sintering-resistant thermal barrier coatings

A thermal barrier coating composition is provided. The composition has a base oxide, a primary stabilizer, and at least two additional cationic oxide dopants. Preferably, a pair of group A and group B defect cluster-promoting oxides is used in conjunction with the base and primary stabilizer oxides. The new thermal barrier coating is found to have significantly lower thermal conductivity and better sintering resistance. In preferred embodiments, the base oxide is selected from zirconia and hafnia. The group A and group B cluster-promoting oxide dopants preferably are selected such that the group A dopant has a smaller cationic radius than the primary stabilizer oxide, and so that the primary stabilizer oxide has a small cationic radius than that of the group B dopant.

Zhu, Dongming↗

NASA NTRS1990

Multilayer ceramic oxide solid electrolyte for fuel cells and electrolysis cells and method for fabrication thereof

An unitary layered ceramic structure is disclosed which comprises co-sintered layers. The co-sintered structure comprises a sintered central layer of yttria stabilized zirconia (YSZ) which is about 8 mole percent yttria and having a density of at least about 95% of theoretical, and sintered outer layers of strontium lanthanum manganite (LSM) having the approximate molecular composition La.sub.0.8 Sr.sub.0.2 MnO.sub.3, having a density from about 50 to about 60% of theoretical, and having interconnected porosity from about 40 to 50% with an interconnected pore diameter from about one micron to about five microns. The sintered central layer is sandwiched by and bonded and sintered to the outer layers and is essentially free of significant amounts of manganese. A process for making the unitary composition-of-matter is also disclosed which involves tape casting a LSM tape and then on top thereof casting a YSZ tape. The process comprises presintering LSM powder at 1250.degree. F., crushing the presintered commercially available LSM powder, forming a slurry with the crushed LSM, a binder and solvent, tape casting the slurry and allowing the slurry to air dry. A mixture of commercially available submicron size particle YSZ powder is milled with a dispersant and solvent to disperse the YSZ particles thereby forming a dispersed YSZ slurry. The YSZ slurry is then tape cast on the dried LSM tape. If desired, a third layer of LSM can be cast on top of the dried YSZ layer. After drying the composite LSM/YSZ and LSM/YSZ/LSM tapes are fired at 1300.degree. C. No migration of manganese into the YSZ layer was observed with scanning electron microscope/edax in the sintered multilayer tape.

Schroeder, James E.↗

NASA NTRS2007

Low conductivity and sintering-resistant thermal barrier coatings

Zhu, Dongming↗

NASA NTRS1990

PdCr Based High Temperature Static Strain Gage

The program at NASA Lewis Research Center to develop a high temperature static strain gage system for the hypersonic vehicle and turbine engine research has emphasized a palladium- 13wt%chromium (PdCr) alloy. Gages made from this alloy are being developed in both fine wire and thin film form. The wire gage system had platinum wire as a temperature compensator and was coated with a special alumina and zirconia mixture overcoat. This PdCr compensated wire gage responded linearly to the imposed strain to at least i000 microstrain. The strain sensitivity of the gage did not vary much with temperature. The apparent strain of this compensated gage was significantly lower than that of the other gages. It varied within 300 microstrain from room temperature to 800 deg. C with a reproducibility within 50 microstrain between thermal cycles to 800 deg. C. This is a significant advance over the 400 deg. C barrier of previous techniques for resistance static strain gages. The sputtered thin film PdCr strain gage, whose size was 8x8 mm and 10 micron thick, has demonstrated the possibility of extending the use of the PdCr strain gage to a temperature of approximately 1000 deg. C.

Lei, Jih-Fen↗

NASA NTRS2008

Monitoring Delamination of Thermal Barrier Coatings by Near-Infrared and Upconversion Luminescence Imaging

Previous work has demonstrated that TBC delamination can be monitored by incorporating a thin luminescent sublayer that produces greatly increased luminescence intensity from delaminated regions of the TBC. Initial efforts utilized visible-wavelength luminescence from either europium or erbium doped sublayers. This approach exhibited good sensitivity to delamination of electron-beam physical-vapor-deposited (EB-PVD) TBCs, but limited sensitivity to delamination of the more highly scattering plasma-sprayed TBCs due to stronger optical scattering and to interference by luminescence from rare-earth impurities. These difficulties have now been overcome by new strategies employing near-infrared (NIR) and upconversion luminescence imaging. NIR luminescence at 1550 nm was produced in an erbium plus ytterbium co-doped yttria-stabilized zirconia (YSZ) luminescent sublayer using 980-nm excitation. Compared to visible-wavelength luminescence, these NIR emission and excitation wavelengths are much more weakly scattered by the TBC and therefore show much improved depth-probing capabilities. In addition, two-photon upconversion luminescence excitation at 980 nm wavelength produces luminescence emission at 562 nm with near-zero fluorescence background and exceptional contrast for delamination indication. The ability to detect TBC delamination produced by Rockwell indentation and by furnace cycling is demonstrated for both EB-PVD and plasma-sprayed TBCs. The relative strengths of the NIR and upconversion luminescence methods for monitoring TBC delamination are discussed.

Eldridge, J. I.↗

NASA NTRS2009

Nanocomposite Strain Gauges Having Small TCRs

Ceramic strain gauges in which the strain-sensitive electrically conductive strips made from nanocomposites of noble metal and indium tin oxide (ITO) are being developed for use in gas turbine engines and other power-generation systems in which gas temperatures can exceed 1,500 F (about 816 C). In general, strain gauges exhibit spurious thermally induced components of response denoted apparent strain. When temperature varies, a strain-gauge material that has a nonzero temperature coefficient of resistance (TCR) exhibits an undesired change in electrical resistance that can be mistaken for the change in resistance caused by a change in strain. It would be desirable to formulate straingauge materials having TCRs as small as possible so as to minimize apparent strain. Most metals exhibit positive TCRs, while most semiconductors, including ITO, exhibit negative TCRs. The present development is based on the idea of using the negative TCR of ITO to counter the positive TCRs of noble metals and of obtaining the benefit of the ability of both ITO and noble metals to endure high temperatures. The noble metal used in this development thus far has been platinum. Combinatorial libraries of many ceramic strain gauges containing nanocomposites of various proportions of ITO and platinum were fabricated by reactive co-sputtering from ITO and platinum targets onto alumina- and zirconia-based substrates mounted at various positions between the targets.

Gregory, Otto↗

NASA NTRS2008

Smart Sensor Systems for Aerospace Applications: From Sensor Development to Application Testing

The application of Smart Sensor Systems for aerospace applications is a multidisciplinary process consisting of sensor element development, element integration into Smart Sensor hardware, and testing of the resulting sensor systems in application environments. This paper provides a cross-section of these activities for multiple aerospace applications illustrating the technology challenges involved. The development and application testing topics discussed are: 1) The broadening of sensitivity and operational range of silicon carbide (SiC) Schottky gas sensor elements; 2) Integration of fire detection sensor technology into a "Lick and Stick" Smart Sensor hardware platform for Crew Exploration Vehicle applications; 3) Extended testing for zirconia based oxygen sensors in the basic "Lick and Stick" platform for environmental monitoring applications. It is concluded that that both core sensor platform technology and a basic hardware platform can enhance the viability of implementing smart sensor systems in aerospace applications.

Hunter, G. W.↗

NASA NTRS2009

Mid-Infrared Reflectance Imaging of Thermal-Barrier Coatings

An apparatus for mid-infrared reflectance imaging has been developed as means of inspecting for subsurface damage in thermal-barrier coatings (TBCs). The apparatus is designed, more specifically, for imaging the progression of buried delamination cracks in plasma-sprayed yttria-stabilized zirconia coatings on turbine-engine components. Progression of TBC delamination occurs by the formation of buried cracks that grow and then link together to produce eventual TBC spallation. The mid-infrared reflectance imaging system described here makes it possible to see delamination progression that is invisible to the unaided eye, and therefore give sufficiently advanced warning before delamination progression adversely affects engine performance and safety. The apparatus (see figure) includes a commercial mid-infrared camera that contains a liquid-nitrogen-cooled focal plane indium antimonide photodetector array, and imaging is restricted by a narrow bandpass centered at wavelength of 4 microns. This narrow wavelength range centered at 4 microns was chosen because (1) it enables avoidance of interfering absorptions by atmospheric OH and CO2 at 3 and 4.25 microns, respectively; and (2) the coating material exhibits maximum transparency in this wavelength range. Delamination contrast is produced in the midinfrared reflectance images because the introduction of cracks into the TBC creates an internal TBC/air-gap interface with a high diffuse reflectivity of 0.81, resulting in substantially higher reflectance of mid-infrared radiation in regions that contain buried delamination cracks. The camera is positioned a short distance (.12 cm) from the specimen. The mid-infrared illumination is generated by a 50-watt silicon carbide source positioned to the side of the mid-infrared camera, and the illumination is collimated and reflected onto the specimen by a 6.35-cm-diameter off-axis paraboloidal mirror. Because the collected images are of a steady-state reflected intensity (in contrast to the transient thermal response observed in infrared thermography), collection times can be lengthened to whatever extent needed to achieve desired signal-to-noise ratios. Each image is digitized, and the resulting data are processed in several steps to obtain a true mid-infrared reflectance image. The raw image includes thermal radiation emitted by the specimen in addition to the desired reflected radiation. The thermal-radiation contribution is eliminated by subtracting the image obtained with the illumination off from the image obtained with the illumination on. A flat-field correction is then made to remove the effects of non-uniformities in the illumination level and pixel-to-pixel variations in sensitivity. This correction is performed by normalizing to an image of a standard object that has a known reflectance at a wavelength of 4 microns. After correction, each pixel value is proportional to the reflectance (at a wavelength of 4-microns) at the corresponding location on the specimen. Mid-infrared reflectance imaging of specimens that were thermally cyc led for different numbers of cycles was performed and demonstrated t hat mid-infrared reflectance imaging was able to monitor the gradual delamination progression that occurs with continued thermal cycling . Reproducible values were obtained for the reflectance associated w ith an attached and fully delaminated TBC, so that intermediate refle ctance values could be interpreted to successfully predict the numbe r of thermal cycles to failure.

Edlridge, Jeffrey I.↗

NASA NTRS2007

Glass/Ceramic Composites for Sealing Solid Oxide Fuel Cells

A family of glass/ceramic composite materials has been investigated for use as sealants in planar solid oxide fuel cells. These materials are modified versions of a barium calcium aluminosilicate glass developed previously for the same purpose. The composition of the glass in mole percentages is 35BaO + 15CaO + 5Al2O3 + 10B2O3 + 35SiO2. The glass seal was found to be susceptible to cracking during thermal cycling of the fuel cells. The goal in formulating the glass/ ceramic composite materials was to (1) retain the physical and chemical advantages that led to the prior selection of the barium calcium aluminosilicate glass as the sealant while (2) increasing strength and fracture toughness so as to reduce the tendency toward cracking. Each of the composite formulations consists of the glass plus either of two ceramic reinforcements in a proportion between 0 and 30 mole percent. One of the ceramic reinforcements consists of alumina platelets; the other one consists of particles of yttria-stabilized zirconia wherein the yttria content is 3 mole percent (3YSZ). In preparation for experiments, panels of the glass/ceramic composites were hot-pressed and machined into test bars.

Bansal, Narottam P.↗

NASA NTRS2007

Multifunctional, High-Temperature Nanocomposites

In experiments conducted as part of a continuing effort to incorporate multifunctionality into advanced composite materials, blends of multi-walled carbon nanotubes and a resin denoted gPETI-330 h (wherein gPETI h is an abbreviation for gphenylethynyl-terminated imide h) were prepared, characterized, and fabricated into moldings. PETI-330 was selected as the matrix resin in these experiments because of its low melt viscosity (<10 poise at a temperature of 280 C), excellent melt stability (lifetime >2 hours at 280 C), and high temperature performance (>1,000 hours at 288 C). The multi-walled carbon nanotubes (MWCNTs), obtained from the University of Kentucky, were selected because of their electrical and thermal conductivity and their small diameters. The purpose of these experiments was to determine the combination of thermal, electrical, and mechanical properties achievable while still maintaining melt processability. The PETI-330/MWCNT mixtures were prepared at concentrations ranging from 3 to 25 weight-percent of MWCNTs by dry mixing of the constituents in a ball mill using zirconia beads. The resulting powders were characterized for degree of mixing and thermal and rheological properties. The neat resin was found to have melt viscosity between 5 and 10 poise. At 280 C and a fixed strain rate, the viscosity was found to increase with time. At this temperature, the phenylethynyl groups do not readily react and so no significant curing of the resin occurred. For MWCNT-filled samples, melt viscosity was reasonably steady at 280 C and was greater in samples containing greater proportions of MWCNTs. The melt viscosity for 20 weightpercent of MWCNTs was found to be .28,000 poise, which is lower than the initial estimated allowable maximum value of 60,000 poise for injection molding. Hence, MWCNT loadings of as much as 20 percent were deemed to be suitable compositions for scale-up. High-resolution scanning electron microscopy (HRSEM) showed the MWCNTs to be well dispersed in the polymer matrices, while high-resolution transmission electron microscopy shows splits in the walls of the MWCNTs but no catastrophic breakage of tubes. To further assess processing characteristics prior to scale-up, samples containing 10, 15, and 20 weight-percent of MWCNTs were processed through a laboratory melting extruder. HRSEM of the extruded fibers shows significant alignment of MWCNTs in the flow direction (see figure). For the samples containing 20 weight-percent of MWCNTs, difficulties were encountered during feeding, and the temperature of a rotor in the extruder rose to 245 C because of buildup of frictional heat; this indicates that materials of this type having MWCNT concentrations .20 weight- percent may not be melt-processable. On the basis of the results from the foregoing characterizations, samples containing 10, 15, and 20 weight-percent of MWCNTs were scaled up to masses of .300 g and used to make specimens having dimensions of 10.2 by 15.2 by 0.32 cm. These specimens were molded by (1) injecting the mixtures, at temperatures between 260 and 280 C, into a tool made of the low-thermal-expansion alloy InvarR and then (2) curing for 1 hour at 371 C. The tool was designed to impart shear during the injection process in an attempt to achieve some alignment of the MWCNTs in the flow direction.

Connell, John W.↗

NASA NTRS2007

Antenna for Measuring Electric Fields Within the Inner Heliosphere

A document discusses concepts for the design of an antenna to be deployed from a spacecraft for measuring the ambient electric field associated with plasma waves at a location within 3 solar radii from the solar photosphere. The antenna must be long enough to extend beyond the photoelectron and plasma sheaths of the spacecraft (expected to be of the order of meters thick) and to enable measurements at frequencies from 20 Hz to 10 MHz without contamination by spacecraft electric-field noise. The antenna must, therefore, extend beyond the thermal protection system (TPS) of the main body of the spacecraft and must withstand solar heating to a temperature as high as 2,000 C while not conducting excessive heat to the interior of the spacecraft. The TPS would be conical and its axis would be pointed toward the Sun. The antenna would include monopole halves of dipoles that would be deployed from within the shadow of the TPS. The outer potion of each monopole would be composed of a carbon-carbon (C-C) composite surface exposed to direct sunlight (hot side) and a C-C side in shadow (cold side) with yttria-stabilized zirconia spacers in-between. The hot side cannot view the spacecraft bus, while the cold side can. The booms also can be tilted to minimize heat input to spacecraft bus. This design allows one to reduce heat input to the spacecraft bus to acceptable levels.

Sittler, Edward Charles↗

NASA NTRS2007

Delamination-Indicating Thermal Barrier Coatings

The risk of premature failure of thermal barrier coatings (TBCs), typically composed of yttria-stabilized zirconia (YSZ), compromises the reliability of TBCs used to provide thermal protection for turbine engine components. Unfortunately, TBC delamination proceeds well beneath the TBC surface and cannot be monitored by visible inspection. Nondestructive diagnostic tools that could reliably probe the subsurface damage state of TBCs would alleviate the risk of TBC premature failure by indicating when the TBC needs to be replaced before the level of TBC damage threatens engine performance or safety. To meet this need, a new coating design for thermal barrier coatings (TBCs) that are self-indicating for delamination has been successfully implemented by incorporating a europium-doped luminescent sublayer at the base of a TBC composed of YSZ. The luminescent sublayer has the same YSZ composition as the rest of the TBC except for the addition of low-level europium doping and therefore does not alter TBC performance.

Eldridge, Jeffrey I.↗

NASA NTRS2010

Fuel-Cell Power Source Based on Onboard Rocket Propellants

The use of onboard rocket propellants (dense liquids at room temperature) in place of conventional cryogenic fuel-cell reactants (hydrogen and oxygen) eliminates the mass penalties associated with cryocooling and boil-off. The high energy content and density of the rocket propellants will also require no additional chemical processing. For a 30-day mission on the Moon that requires a continuous 100 watts of power, the reactant mass and volume would be reduced by 15 and 50 percent, respectively, even without accounting for boiloff losses. The savings increase further with increasing transit times. A high-temperature, solid oxide, electrolyte-based fuel-cell configuration, that can rapidly combine rocket propellants - both monopropellant system with hydrazine and bi-propellant systems such as monomethyl hydrazine/ unsymmetrical dimethyl hydrazine (MMH/UDMH) and nitrogen tetroxide (NTO) to produce electrical energy - overcomes the severe drawbacks of earlier attempts in 1963-1967 of using fuel reforming and aqueous media. The electrical energy available from such a fuel cell operating at 60-percent efficiency is estimated to be 1,500 Wh/kg of reactants. The proposed use of zirconia-based oxide electrolyte at 800-1,000 C will permit continuous operation, very high power densities, and substantially increased efficiency of conversion over any of the earlier attempts. The solid oxide fuel cell is also tolerant to a wide range of environmental temperatures. Such a system is built for easy refueling for exploration missions and for the ability to turn on after several years of transit. Specific examples of future missions are in-situ landers on Europa and Titan that will face extreme radiation and temperature environments, flyby missions to Saturn, and landed missions on the Moon with 14 day/night cycles.

Ganapathi, Gani↗

NASA NTRS2010

Combined Heat Transfer in High-Porosity High-Temperature Fibrous Insulations: Theory and Experimental Validation

Combined radiation and conduction heat transfer through various high-temperature, high-porosity, unbonded (loose) fibrous insulations was modeled based on first principles. The diffusion approximation was used for modeling the radiation component of heat transfer in the optically thick insulations. The relevant parameters needed for the heat transfer model were derived from experimental data. Semi-empirical formulations were used to model the solid conduction contribution of heat transfer in fibrous insulations with the relevant parameters inferred from thermal conductivity measurements at cryogenic temperatures in a vacuum. The specific extinction coefficient for radiation heat transfer was obtained from high-temperature steady-state thermal measurements with large temperature gradients maintained across the sample thickness in a vacuum. Standard gas conduction modeling was used in the heat transfer formulation. This heat transfer modeling methodology was applied to silica, two types of alumina, and a zirconia-based fibrous insulation, and to a variation of opacified fibrous insulation (OFI). OFI is a class of insulations manufactured by embedding efficient ceramic opacifiers in various unbonded fibrous insulations to significantly attenuate the radiation component of heat transfer. The heat transfer modeling methodology was validated by comparison with more rigorous analytical solutions and with standard thermal conductivity measurements. The validated heat transfer model is applicable to various densities of these high-porosity insulations as long as the fiber properties are the same (index of refraction, size distribution, orientation, and length). Furthermore, the heat transfer data for these insulations can be obtained at any static pressure in any working gas environment without the need to perform tests in various gases at various pressures.

Daryabeigi, Kamran↗

NASA NTRS2000

The 2001 Mars In-Situ-Propellant-Production Precursor (MIP) Flight Demonstration

The successful performance of the five individual demonstrations of MARS IN-SITU-PROPELLANT-PRODUCTION PRECURSOR (MIP) will provide both knowledge of and confidence in the reliability of this technology. At the completion of this flight demonstration, the MIP Team will be able to: a) recommend preferred hardware configurations for the intake and adsorption of carbon dioxide from the Martian atmosphere; b) understand the performance characteristics of zirconia cells to generate propellant-grade oxygen; c) understand long-term performance characteristics of advanced solar cells/arrays operated in the actual Mars environment; d) evaluate the functionality of methods to mitigate the deposition of airborne dust onto solar arrays; and e) recommend preferred hardware designs for innovative thermal management including the radiation of heat to the outside environment.

Kaplan, David I.↗

NASA NTRS2011

Monitoring Delamination of Thermal Barrier Coating During Interrupted High-Heat Flux Laser Testing Using Upconversion Luminescence Imaging

Upconversion luminescence imaging of thermal barrier coatings (TBCs) has been shown to successfully monitor TBC delamination progression during interrupted furnace cycling. However, furnace cycling does not adequately model engine conditions where TBC-coated components are subjected to significant heat fluxes that produce through-thickness temperature gradients that may alter both the rate and path of delamination progression. Therefore, new measurements are presented based on luminescence imaging of TBC-coated specimens subjected to interrupted high-heat-flux laser cycling exposures that much better simulate the thermal gradients present in engine conditions. The TBCs tested were deposited by electron-beam physical vapor deposition (EB-PVD) and were composed of 7wt% yttria-stabilized zirconia (7YSZ) with an integrated delamination sensing layer composed of 7YSZ co-doped with erbium and ytterbium (7YSZ:Er,Yb). The high-heat-flux exposures that produce the desired through-thickness thermal gradients were performed using a high power CO2 laser operating at a wavelength of 10.6 microns. Upconversion luminescence images revealed the debond progression produced by the cyclic high-heat-flux exposures and these results were compared to that observed for furnace cycling.

Eldridge, Jeffrey I.↗

NASA NTRS2011

Plasma Spray-Physical Vapor Deposition (PS-PVD) of Ceramics for Protective Coatings

In order to generate advanced multilayer thermal and environmental protection systems, a new deposition process is needed to bridge the gap between conventional plasma spray, which produces relatively thick coatings on the order of 125-250 microns, and conventional vapor phase processes such as electron beam physical vapor deposition (EB-PVD) which are limited by relatively slow deposition rates, high investment costs, and coating material vapor pressure requirements. The use of Plasma Spray - Physical Vapor Deposition (PS-PVD) processing fills this gap and allows thin (< 10 microns) single layers to be deposited and multilayer coatings of less than 100 microns to be generated with the flexibility to tailor microstructures by changing processing conditions. Coatings of yttria-stabilized zirconia (YSZ) were applied to NiCrAlY bond coated superalloy substrates using the PS-PVD coater at NASA Glenn Research Center. A design-of-experiments was used to examine the effects of process variables (Ar/He plasma gas ratio, the total plasma gas flow, and the torch current) on chamber pressure and torch power. Coating thickness, phase and microstructure were evaluated for each set of deposition conditions. Low chamber pressures and high power were shown to increase coating thickness and create columnar-like structures. Likewise, high chamber pressures and low power had lower growth rates, but resulted in flatter, more homogeneous layers

Harder, Bryan J.↗

NASA NTRS2006

Lower-Conductivity Ceramic Materials for Thermal-Barrier Coatings

Doped pyrochlore oxides of a type described below are under consideration as alternative materials for high-temperature thermal-barrier coatings (TBCs). In comparison with partially-yttria-stabilized zirconia (YSZ), which is the state-of-the-art TBC material now in commercial use, these doped pyrochlore oxides exhibit lower thermal conductivities, which could be exploited to obtain the following advantages: For a given difference in temperature between an outer coating surface and the coating/substrate interface, the coating could be thinner. Reductions in coating thicknesses could translate to reductions in weight of hot-section components of turbine engines (e.g., combustor liners, blades, and vanes) to which TBCs are typically applied. For a given coating thickness, the difference in temperature between the outer coating surface and the coating/substrate interface could be greater. For turbine engines, this could translate to higher operating temperatures, with consequent increases in efficiency and reductions in polluting emissions. TBCs are needed because the temperatures in some turbine-engine hot sections exceed the maximum temperatures that the substrate materials (superalloys, Si-based ceramics, and others) can withstand. YSZ TBCs are applied to engine components as thin layers by plasma spraying or electron-beam physical vapor deposition. During operation at higher temperatures, YSZ layers undergo sintering, which increases their thermal conductivities and thereby renders them less effective as TBCs. Moreover, the sintered YSZ TBCs are less tolerant of stress and strain and, hence, are less durable.

Bansal, Narottam P.↗