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NASA NTRS2001

Thermal Barrier Coatings for Airfoil Applications

Thermal barrier coatings having sigruficantly reduced thermal conductivities are being developed under this program. The conductivities, after 20 hours of sintering under high heat flux exposure in a unique laser rig test, are reduced to nearly 1/3 of the state-of-the-art baseline value for the plasma sprayed coatings and to 1/2 of the baseline for the physical vapor-deposited coatings. The coatings consist of zirconia-yttria with relatively small additions of certain rare earth oxides. Further conductivity reductions and cyclic life optimization are planned for the coming year.

Miller, Robert A.↗

NASA NTRS2003

Low Thermal Conductivity Thermal Barrier Coatings Developed

Thermal barrier coatings (TBCs) are used extensively in modern gas turbine engines to thermally insulate air-cooled metallic components from the hot gases in the engine. These coatings typically consist of a zirconia-yttria ceramic that has been applied by either plasma spraying or physical vapor deposition. Future engines will rely even more heavily on TBCs and will require materials that have even higher temperature capability with improved insulation (i.e., lower thermal conductivity even after many hours at high temperature). This report discusses new TBCs that have been developed with these future requirements in mind. The Ultra-Efficient Engine Technology Program at the NASA Glenn Research Center is funding this effort, which has been conducted primarily at Glenn with contractor support (GE and Howmet) for physical vapor deposition. As stated, the new TBC not only had to be more insulating but the insulation had to persist even after many hours of exposure-that is, the new TBC had to have both lower conductivity and improved sintering resistance. A new type of test rig was developed for this task. This new test approach used a laser to deliver a known high heat flux in an essentially uniform pattern to the surface of the coating, thereby establishing a realistic thermal gradient across its thickness. This gradient was determined from surface and backside pyrometry; and since the heat flux and coating thickness are known, this permitted continuous monitoring of thermal conductivity. Thus, this laser rig allowed very efficient screening of candidate low-conductivity, sinter-resistant TBCs. The coating-design approach selected for these new low-conductivity TBCs was to identify oxide dopants that had the potential to promote the formation of relatively large and stable groupings of defects known as defect clusters. This approach was used because it was felt that such clusters would reduce conductivity while enhancing stability. The approach proved to be successful: low-conductivity TBCs having improved sintering resistance were developed.

Zhu, Dongming↗

NASA NTRS2003

Multiwavelength Pyrometer Developed for Use at Elevated Temperatures in Aerospace Applications

Researchers at the NASA Glenn Research Center have developed a unique multiwavelength pyrometer for aerospace applications. It has been shown to be a useful and versatile instrument for measuring the surface temperatures of ceramic zirconia thermal barrier coatings (TBCs) and alumina, even when their emissivity is unknown. The introduction of fiber optics into the pyrometer has greatly increased the ease of using this instrument. Direct comparison of measurements obtained using the pyrometer and thin film thermocouples on a sample provided independent verification of pyrometry temperature measurement. Application of the pyrometer has also included simultaneous surface and bulk temperature measurement in a transparent material, the measurement of combustion gas temperatures in the flames of an atmospheric burner, the measurement of the temperature distribution appearing on a large surface from the recording of just a single radiation spectrum emitted from this nonuniform temperature surface, and the measurement of some optical properties for special aeronautical materials-such as nanostructured layers. The multiwavelength pyrometer temperature is obtained from a radiation spectrum recorded over a broad wavelength region by transforming it into a straight line segment(s) in part or all of the spectral region. The intercept of the line segment(s) with the vertical axis at zero wavelength gives the inverse of the temperature. In a two-color pyrometer, the two data points are also amenable to this analysis to determine the unknown temperature. Implicit in a two-color pyrometer is the assumption of wavelength-independent emissivity. Its two (and minimum) pieces of data are sufficient to determine this straight line. However, a multiwavelength pyrometer not only has improved accuracy but also confirms that the wavelength-independent emissivity assumption is valid when a multitude of data points are shown to lie on a simple straight line.

Ng, Daniel L.↗

NASA NTRS2005

Crack Driving Forces in a Multilayered Coating System for Ceramic Matrix Composite Substrates

The effects of the top coating thickness, modulus and shrinkage strains on the crack driving forces for a baseline multilayer Yttria-Stabilized-Zirconia/Mullite/Si thermal and environment barrier coating (TEBC) system for SiC/SiC ceramic matrix composite substrates are determined for gas turbine applications. The crack driving forces increase with increasing modulus, and a low modulus thermal barrier coating material (below 10 GPa) will have no cracking issues under the thermal gradient condition analyzed. Since top coating sintering increases the crack driving forces with time, highly sintering resistant coatings are desirable to maintain a low tensile modulus and maintain a low crack driving force with time. Finite element results demonstrated that an advanced TEBC system, such as ZrO2/HfO2, which possesses improved sintering resistance and high temperature stability, exhibited excellent durability. A multi-vertical cracked structure with fine columnar spacing is an ideal strain tolerant coating capable of reducing the crack driving forces to an acceptable level even with a high modulus of 50 GPa.

Ghosn, Louis J.↗

NASA NTRS2005

Low-Thermal-Conductivity Pyrochlore Oxide Materials Developed for Advanced Thermal Barrier Coatings

When turbine engines operate at higher temperatures, they consume less fuel, have higher efficiencies, and have lower emissions. The upper-use temperatures of the base materials (superalloys, silicon-based ceramics, etc.) used for the hot-section components of turbine engines are limited by the physical, mechanical, and corrosion characteristics of these materials. Thermal barrier coatings (TBCs) are applied as thin layers on the surfaces of these materials to further increase the operating temperatures. The current state-of-the-art TBC material in commercial use is partially yttria-stabilized zirconia (YSZ), which is applied on engine components by plasma spraying or by electron-beam physical vapor deposition. At temperatures higher than 1000 C, YSZ layers are prone to sintering, which increases thermal conductivity and makes them less effective. The sintered and densified coatings can also reduce thermal stress and strain tolerance, which can reduce the coating s durability significantly. Alternate TBC materials with lower thermal conductivity and better sintering resistance are needed to further increase the operating temperature of turbine engines.

Bansal, Narottam P.↗

NASA NTRS2005

VPS Process for Copper Components in Thrust Chamber Assemblies

For several years, NASA's Marshall Space Flight Center (MSFC) has been working with Plasma Processes, Inc., (PPI) to fabricate thrust chamber liners with GRCop-84. Using the vacuum plasma spray (VPS) process, chamber liners of a variety of shapes and sizes have been created. Each has been formed as a functional gradient material (FGM) that creates a unique protective layer of NiCrAlY on the GRCop-84 liner s hot wall surface. Hot-fire testing was successfully conducted on a subscale unit to demonstrate the liner's durability and performance. Similar VPS technology has also been applied to create functional gradient coatings (FGC) on copper injector faceplates. Protective layers of NiCrAlY and zirconia were applied to both coaxial and impinging faceplate designs. Hot-fire testing is planned for these coated injectors in April 2005. The resulting material systems for both copper alloy components allows them to operate at higher temperatures with improved durability and operating margins.

Elam, Sandra↗

NASA NTRS2006

Vacuum Plasma Spray (VPS) Material Applications for Thruster Components

A variety of vacuum plasma spray (VPS) material systems have been successfully applied to injector and thrust chamber components. VPS offers a versatile fabrication process with relatively low costs to produce near net shape parts. The materials available with VPS increase operating margins and improve component life by providing superior thermal and oxidation protection in specific engine environments. Functional gradient materials (FGM) formed with VPS allow thrust chamber liners to be fabricated with GRCop-84 (an alloy of copper, chrome, and niobium) and a protective layer of NiCrAlY on the hot wall. A variety of thrust chamber liner designs have been fabricated to demonstrate the versatility of the process. Hot-fire test results have confirmed the improved durability and high temperature performance of the material systems for thrust chamber liners. Similar FGM s have been applied to provide superior thermal protection on injector faceplates with NiCrAlY and zirconia coatings. The durability of the applied materials has been demonstrated with hot-fire cycle testing on injector faceplates in high temperature environments. The material systems can benefit the components used in booster and main engine propulsion systems. More recent VPS efforts are focused on producing rhenium based material systems for high temperature applications to benefit in-space engines like reaction control system (RCS) thrusters.

Elam, Sandra↗

NASA NTRS2006

Vacuum Plasma Spray (VPS) Material Applications for Thruster Components

A variety of vacuum plasma spray (VPS) material systems have been successfully applied to injector and thrust chamber components. VPS offers a versatile fabrication process with relatively low costs to produce near net shape parts. The materials available with VPS increase operating margins and improve component life by providing superior thermal and oxidation protection in specific engine environments. Functional gradient materials (FGM) formed with VPS allow thrust chamber liners to be fabricated with GRCop-84 (an alloy of copper, chrome, and niobium) and a protective layer of NiCrAlY on the hot wall. A variety of thrust chamber liner designs have been fabricated to demonstrate the versatility of the process. Hot-fire test results have confined the improved durability and high temperature performance of the material systems for thrust chamber liners. Similar FGM s have been applied to provide superior thermal protection on injector faceplates with NiCrAlY and zirconia coatings. The durability of the applied materials has been demonstrated with hot-fire cycle testing on injector faceplates in high temperature environments. The material systems can benefit the components used in booster and main engine propulsion systems. More recent VPS efforts are focused on producing rhenium based material systems for high temperature applications to benefit in-space engines like reaction control system (RCS) thrusters.

Elam, Sandra↗

NASA NTRS2007

Detecting Thermal Barrier Coating Delamination Using Visible and Near-Infrared Luminescence from Erbium-Doped Sublayers

Nondestructive diagnostic tools are needed to monitor early stages of delamination progression in thermal barrier coatings (TBCs) because the risk of delamination induced coating failure will compromise engine performance and safety. Previous work has demonstrated that for TBCs composed of yttria-stabilized zirconia (YSZ), luminescence from a buried europium-doped sublayer can be utilized to identify the location of TBC delamination from the substantially higher luminescence intensity observed from the delaminated regions of the TBC. Luminescence measurements from buried europium-doped layers depend on sufficient transmittance of the 532 nm excitation and 606 nm emission wavelengths through the attenuating undoped YSZ overlayer to produce easily detected luminescence. In the present work, improved delamination indication is demonstrated using erbium-doped YSZ sublayers. For visible-wavelength luminescence, the erbium-doped sublayer offers the advantage of a very strong excitation peak at 517 nm that can be conveniently excited a 514 nm Ar ion laser. More importantly, the erbium-doped sublayer also produces near-infrared luminescence at 1550 nm that is effectively excited by a 980 nm laser diode. Both the 980 nm excitation and the 1550 nm emission are transmitted through the TBC with much less attenuation than visible wavelengths and therefore show great promise for delamination monitoring through thicker or more highly scattering TBCs. The application of this approach for both electron beam physical vapor deposited (EB-PVD) and plasma-sprayed TBCs is discussed.

Eldridge, J. I.↗

NASA NTRS2007

Concurrent CO2 Control and O2 Generation for Advanced Life Support

The electrochemical reduction of carbon dioxide (CO2) using ceramic oxygen generators (COGs) is well known and widely studied, however, conventional devices using yttria-stabilized zirconia (YSZ) electrolytes operate at temperatures greater than 700 C. Operating at such high temperatures increases system mass compared to lower temperature systems because of increased energy overhead to get the COG up to operating temperature and the need for heavier insulation and/or heat exchangers to reduce the COG oxygen (O2) output temperature for comfortable inhalation. Recently, the University of Florida developed novel ceramic oxygen generators employing a bilayer electrolyte of gadolinia-doped ceria and erbia-stabilized bismuth for NASA's future exploration of Mars. To reduce landed mass and operation expenditures during the mission, in-situ resource utilization was proposed using these COGs to obtain both lifesupporting oxygen and oxidant/propellant fuel, by converting CO2 from the Mars atmosphere. The results showed that oxygen could be reliably produced from CO2 at temperatures as low as 400 C. These results indicate that this technology could be adapted to CO2 removal from a spacesuit and other applications in which CO2 removal was an issue. The strategy proposed for CO2 removal for advanced life support systems employs a catalytic layer combined with a COG so that it is reduced all the way to solid carbon and oxygen. Hence, a three-phased approach was used for the development of a viable low weight COG for CO2 removal. First, to reduce the COG operating temperature a high oxide ion conductivity electrolyte was developed. Second, to promote full CO2 reduction while avoiding the problem of carbon deposition on the COG cathode, novel cathodes and a removable catalytic carbon deposition layer were designed. Third, to improve efficiency, a pre-stage for CO2 absorption was used to concentrate CO2 from the exhalate before sending it to the COG. These subsystems were then integrated into a single CO2 removal system. This paper describes our progress to date on these tasks.

Paul, Heather L.↗

NASA NTRS2007

Oxygen Generation from Carbon Dioxide for Advanced Life Support

The partial electrochemical reduction of CO2 using ceramic oxygen generators (COGs) is well known and has been studied. Conventional COGs use yttria-stabilized zirconia (YSZ) electrolytes and operate at temperatures greater than 700 C (1, 2). Operating at a lower temperature has the advantage of reducing the mass of the ancillary components such as insulation. Moreover, complete reduction of metabolically produced CO2 (into carbon and oxygen) has the potential of reducing oxygen storage weight if the oxygen can be recovered. Recently, the University of Florida developed ceramic oxygen generators employing a bilayer electrolyte of gadolinia-doped ceria and erbia-stabilized bismuth oxide (ESB) for NASA s future exploration of Mars (3). The results showed that oxygen could be reliably produced from CO2 at temperatures as low as 400 C. These results indicate that this technology could be adapted to CO2 removal from a spacesuit and other applications in which CO2 removal is an issue. This strategy for CO2 removal in advanced life support systems employs a catalytic layer combined with a COG so that the CO2 is reduced completely to solid carbon and oxygen. First, to reduce the COG operating temperature, a thin, bilayer electrolyte was employed. Second, to promote full CO2 reduction while avoiding the problem of carbon deposition on the COG cathode, a catalytic carbon deposition layer was designed and the cathode utilized materials shown to be coke resistant. Third, a composite anode was used consisting of bismuth ruthenate (BRO) and ESB that has been shown to have high performance (4). The inset of figure 1 shows the conceptual design of the tubular COG and the rest of the figure shows schematically the test apparatus. Figure 2 shows the microstructure of a COG tube prior to testing. During testing, current is applied across the cell and initially CuO is reduced to copper metal by electrochemical pumping. Then the oxygen source becomes the CO/CO2. This presentation details the results of testing the COG.

Bishop, s. R.↗

NASA NTRS2006

Monitoring Delamination of Plasma-Sprayed Thermal Barrier Coatings by Reflectance-Enhanced Luminescence

Highly scattering plasma-sprayed thermal barrier coatings (TBCs) present a challenge for optical diagnostic methods to monitor TBC delamination because scattering attenuates light transmitted through the TBC and usually degrades contrast between attached and delaminated regions of the TBC. This paper presents a new approach where reflectance-enhanced luminescence from a luminescent sublayer incorporated along the bottom of the TBC is used to identify regions of TBC delamination. Because of the higher survival rate of luminescence reflecting off the back surface of a delaminated TBC, the strong scattering exhibited by plasma-sprayed TBCs actually accentuates contrast between attached and delaminated regions by making it more likely that multiple reflections of luminescence off the back surface occur before exiting the top surface of the TBC. A freestanding coating containing sections designed to model an attached or delaminated TBC was prepared by depositing a luminescent Eu-doped or Er-doped yttria-stabilized zirconia (YSZ) luminescent layer below a plasma-sprayed undoped YSZ layer and utilizing a NiCr backing layer to represent an attached substrate. For specimens with a Eu-doped YSZ luminescent sublayer, luminescence intensity maps showed excellent contrast between unbacked and NiCr-backed sections even at a plasma-sprayed overlayer thickness of 300 m. Discernable contrast between unbacked and NiCr-backed sections was not observed for specimens with a Er-doped YSZ luminescent sublayer because luminescence from Er impurities in the undoped YSZ layer overwhelmed luminescence originating form the Er-doped YSZ sublayer.

Eldridge, Jeffrey I.↗

NASA NTRS1991

Multilayer ceramic oxide solid electrolyte for fuel cells and electrolysis cells

A 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 NTRS1995

Guanidine based vehicle/binders for use with oxides, metals and ceramics

The use of guanidine salts of organic fatty acids (guanidine soaps) as vehicles and binders for coating substrate surfaces is disclosed. Being completely organic, the guanidine soaps can be burned off leaving no undesirable residue. Of special interest is the use of guanidine 2-ethyl hexanoate as the vehicle and binder for coating problematic surfaces such as in coating alumina fibers with platinum or zirconia. For this application the guanidine soap is used as a melt. For other applications the guanidine soap may be used in a solution with a variety of solvents, the solution containing chlorometalates or powdered metals, refractories or ceramics.

Philipp, Warren H.↗

NASA NTRS1995

Spacecraft ceramic protective shield

A low areal density protective shield apparatus, and method for making same, for protecting spacecraft structures from impact with hypervelocity objects, including a bumper member comprising a bumper ceramic layer, a bumper shock attenuator layer, and a bumper confining layer. The bumper ceramic layer can be SiC or B.sub.4 C; the bumper shock attenuator layer can be zirconia felt; and the bumper confining layer can be aluminum. A base armor member can be spaced from the bumper member and a ceramic fiber-based curtain can be positioned between the bumper and base armor members.

Larriva, Rene F.↗

NASA NTRS2000

Monolithic integrated high-T.sub.c superconductor-semiconductor structure

A method for the fabrication of active semiconductor and high-temperature superconducting device of the same substrate to form a monolithically integrated semiconductor-superconductor (MISS) structure is disclosed. A common insulating substrate, preferably sapphire or yttria-stabilized zirconia, is used for deposition of semiconductor and high-temperature superconductor substructures. Both substructures are capable of operation at a common temperature of at least 77 K. The separate semiconductor and superconductive regions may be electrically interconnected by normal metals, refractory metal silicides, or superconductors. Circuits and devices formed in the resulting MISS structures display operating characteristics which are equivalent to those of circuits and devices prepared on separate substrates.

Burns, Michael J.↗

NASA NTRS2004

Low conductivity and sintering-resistant thermal barrier coatings

A thermal barrier coating composition comprising a base oxide, a primary stabilizer oxide, and at least one dopant oxide is disclosed. 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. The base oxide is selected from the group consisting of zirconia and hafnia and combinations thereof. The primary stabilizing oxide is selected from the group consisting of yttria, dysprosia, erbia and combinations thereof. The dopant or group A and group B cluster-promoting oxide dopants are selected from the group consisting of rare earth metal oxides, transitional metal oxides, alkaline earth metal oxides and combinations thereof. The dopant or dopants preferably have ionic radii different from those of the primary stabilizer and/or the base oxides.

Zhu, Dongming↗

NASA NTRS2000

Method for making a monolithic integrated high-T.sub.c superconductor-semiconductor structure

A method for the fabrication of active semiconductor and high-temperature perconducting devices on the same substrate to form a monolithically integrated semiconductor-superconductor (MISS) structure is disclosed. A common insulating substrate, preferably sapphire or yttria-stabilized zirconia, is used for deposition of semiconductor and high-temperature superconductor substructures. Both substructures are capable of operation at a common temperature of at least 77 K. The separate semiconductor and superconductive regions may be electrically interconnected by normal metals, refractory metal silicides, or superconductors. Circuits and devices formed in the resulting MISS structures display operating characteristics which are equivalent to those of circuits and devices prepared on separate substrates.

Burns, Michael J.↗