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NASA NTRS2004

Formulations for Stronger Solid Oxide Fuel-Cell Electrolytes

Tests have shown that modification of chemical compositions can increase the strengths and fracture toughnesses of solid oxide fuel-cell (SOFC) electrolytes. Heretofore, these solid electrolytes have been made of yttria-stabilized zirconia, which is highly conductive for oxygen ions at high temperatures, as needed for operation of fuel cells. Unfortunately yttria-stabilized zirconia has a high coefficient of thermal expansion, low resistance to thermal shock, low fracture toughness, and low mechanical strength. The lack of strength and toughness are especially problematic for fabrication of thin SOFC electrolyte membranes needed for contemplated aeronautical, automotive, and stationary power-generation applications. The modifications of chemical composition that lead to increased strength and fracture toughness consist in addition of alumina to the basic yttria-stabilized zirconia formulations. Techniques for processing of yttria-stabilized zirconia/alumina composites containing as much as 30 mole percent of alumina have been developed. The composite panels fabricated by these techniques have been found to be dense and free of cracks. The only material phases detected in these composites has been cubic zirconia and a alumina: this finding signifies that no undesired chemical reactions between the constituents occurred during processing at elevated temperatures. The flexural strengths and fracture toughnesses of the various zirconia-alumina composites were measured in air at room temperature as well as at a temperature of 1,000 C (a typical SOFC operating temperature). The measurements showed that both flexural strength and fracture toughness increased with increasing alumina content at both temperatures. In addition, the modulus of elasticity and the thermal conductivity were found to increase and the density to decrease with increasing alumina content. The oxygen-ion conductivity at 1,000 C was found to be unchanged by the addition of alumina.

Bansal, Narottam P.↗

NASA NTRS1978

Effects of compositional changes on the performance of a thermal barrier coating system

Currently proposed thermal barrier systems for aircraft gas turbine engines consist of NiCrAlY bond coating covered with an insulating oxide layer of yttria-stabilized zirconia. The effect of yttrium concentration (from 0.15 to 1.08 w/o) in the bond coating and the yttria concentration (4 to 24.4 w/o) in the oxide layer were evaluated. Furnace, natural gas-oxygen torch, and Mach 1.0 burner rig cyclic tests on solid specimens and air-cooled blades were used to identify trends in coating behavior. Results indicate that the combinations of yttrium levels between 0.15 - 0.35 w/o in the bond coating and the yttria concentration between 6 - 8 w/o in the zirconium oxide layer were the most adherent and resistant to high temperature cyclic exposure.

Stecura, S.↗

NASA NTRS2003

Lower-Conductivity Thermal-Barrier Coatings

Thermal-barrier coatings (TBCs) that have both initial and post-exposure thermal conductivities lower than those of yttria-stabilized zirconia TBCs have been developed. TBCs are thin ceramic layers, generally applied by plasma spraying or physical vapor deposition, that are used to insulate air-cooled metallic components from hot gases in gas turbine and other heat engines. Heretofore, yttria-stabilized zirconia (nominally comprising 95.4 atomic percent ZrO2 + 4.6 atomic percent Y2O3) has been the TBC material of choice. The lower-thermal-conductivity TBCs are modified versions of yttria-stabilized zirconia, the modifications consisting primarily in the addition of other oxides that impart microstructural and defect properties that favor lower thermal conductivity.

Miller, Robert A.↗

NASA NTRSDate not supplied

Quick and Correlative TOF-SIMS Analysis of Dispersoid Content in Powder Feedstock and Printed Oxide Dispersion Strengthened Alloys

Oxide dispersion strengthening (ODS) of metal alloys, when combined with additive manufacturing (AM), can be used to solve high-temperature material application problems. The performance of ODS materials is dependent on nano-scale oxide being distributed uniformly throughout the metal matrix; a homogenous distribution is critical to the creep and yield strength. Therefore, quantifying and analyzing these oxide nanoparticles is essential for ODS alloy development. Assessing the chemistry and morphology of dispersoids in a material can be conducted using a variety of X-ray and electron-based methods. Time of Flight Secondary Ion Mass Spectrometry (TOF-SIMS), which assesses chemical concentrations from ion masses, provides the necessary spatial resolution and avoids potential spectral overlap of all elements present. In this work, preparing ODS powder feedstock and Laser Powder Bed Fusion AM was conducted with a NiCoCr alloy and yttria dispersoid, mixed with a Resodyn resonance mixer and printed on an EOS M100 3D printer at NASA Glenn. TOF-SIMS was performed on a Physical Electronics NanoTOF TRIFT V TOF-SIMS at Case Western Reserve University. The TOF-SIMS results collected on the feedstock powder samples correspond to the qualitative interpretation of the homogeneity of the oxide coating on the metal powder from SEM images. This provides quantitative support to the qualitative microscopy images collected earlier in the process design phase. The variance in the yttrium distribution on the powder feedstock samples also correlated with the variance of the yttrium distribution detected in the printed samples. This correlation supported the hypothesis that an even coating of yttria on the metal powders contributes to an even distribution of yttria in the printed material.

Laura G. Wilson↗

NASA NTRS1976

Ceramic thermal-barrier coatings for cooled turbines

Coating systems consisting of a plasma sprayed layer of zirconia stabilized with either yttria, magnesia or calcia over a thin alloy bond coat have been developed, their potential was analyzed and their durability and benefits evaluated in a turbojet engine. The coatings on air cooled rotating blades were in good condition after completing as many as 500 two-minute cycles of engine operation between full power at a gas temperature of 1644 K and flameout, or as much as 150 hours of steady state operation on cooled vanes and blades at gas temperatures as high as 1644 K with 35 start and stop cycles. On the basis of durability and processing cost, the yttria stabilized zirconia was considered the best of the three coatings investigated.

Liebert, C. H.↗

NASA NTRS1976

Durability of zirconia thermal-barrier ceramic coatings on air-cooled turbine blades in cyclic jet engine operation

Thermal barrier ceramic coatings of stabilized zirconia over a bond coat of Ni Cr Al Y were tested for durability on air cooled turbine rotor blades in a research turbojet engine. Zirconia stabilized with either yttria, magnesia, or calcia was investigated. On the basis of durability and processing cost, the yttria stabilized zirconia was considered the best of the three coatings investigated.

Liebert, C. H.↗

NASA NTRS1976

Ceramic thermal-barrier coatings for cooled turbines

Ceramic thermal-barrier coatings on hot engine parts have the potential to reduce metal temperatures, coolant requirements, cost, and complexity of the cooling configuration, and to increase life, turbine efficiency and gas temperature. Coating systems consisting of a plasma-sprayed layer of zirconia stabilized with either yttria, magnesia or calcia over a thin alloy bond coat have been developed, their potential analyzed and their durability and benefits evaluated in a turbojet engine. The coatings on air-cooled rotating blades were in good condition after completing as many as 500 two-minute cycles of engine operation between full power at a gas temperature of 1644 K and flameout, or as much as 150 hours of steady-state operation on cooled vanes and blades at gas temperatures as high as 1644 K witn 35 start and stop cycles. On the basis of durability and processing cost, the yttria-stabilized zirconia was considered the best of the three coatings investigated.

Liebert, C. H.↗

NASA NTRS1981

Thermal barrier coatings for thermal insulation and corrosion resistance in industrial gas turbine engines

Four thermal barrier coatings were subjected to a 500-hour gas turbine engine test. The coatings were two yttria stabilized zirconias, calcium ortho silicate and calcium meta titanate. The calcium silicate coating exhibited significant spalling. Yttria stabilized zirconia and calcium titanate coatings showed little degradation except in blade leading edge areas. Post-test examination showed variations in the coating due to manual application techniques. Improved process control is required if engineering quality coatings are to be developed. The results indicate that some leading edge loss of the coating can be expected near the tip.

Vogan, J. W.↗

NASA NTRS1982

Two-layer thermal-barrier systems for Ni-Al-Mo alloy and effects of alloy thermal expansion on system life

Cyclic furnace and cyclic natural gas-oxygen torch rig tests were conducted to (1) identify a thermal-barrier system for a nickel-aluminum-molybdenum alloy, (2) study the oxidation of the bond coating, and (3) study the effect of the substrate coefficient of thermal expansion on thermal barrier system life. It is found that the latter is affected by the composition of the bond coating, yttria concentration in zirconia, and the coefficient of thermal expansion of the substrate material. In addition, small compositional changes in the bond and thermal barrier coatings have greater effect on thermal barrier system life than the 40% increase in the coefficient of thermal expansion of the substrate material. No simple relation exists between the weight gain caused by bond-coating oxidation with increasing yttria concentration in zirconia and increasing bond coating thickness on the one hand, and thermal barrier system life on the other.

Stecura, S.↗

NASA NTRS1982

JT90 thermal barrier coated vanes

The technology of plasma sprayed thermal barrier coatings applied to turbine vane platforms in modern high temperature commercial engines was advanced to the point of demonstrated feasibility for application to commercial aircraft engines. The three thermal barrier coatings refined under this program are zirconia stabilized with twenty-one percent magnesia (21% MSZ), six percent yttria (6% YSZ), and twenty percent yttria (20% YSZ). Improvement in thermal cyclic endurance by a factor of 40 times was demonstrated in rig tests. A cooling system evolved during the program which featured air impingement cooling for the vane platforms rather than film cooling. The impingement cooling system, in combination with the thermal barrier coatings, reduced platform cooling air requirements by 44% relative to the current film cooling system. Improved durability and reduced cooling air requirements were demonstrated in rig and engine endurance tests. Two engine tests were conducted, one of 1000 cycles and the other of 1500 cycles. All three coatings applied to vanes fabricated with the final cooling system configuration completed the final 1500 cycle engine endurance test. Results of this test clearly demonstrated the durability of the 6% YSZ coating which was in very good condition after the test. The 21% MSZ and 20% YSZ coatings had numerous occurrences of significant spalling in the test.

Sheffler, K. D.↗

NASA NTRS1985

Long-term stability and properties of zirconia ceramics for heavy duty diesel engine components

Physical, mechanical, and thermal properties of commercially available transformation-toughened zirconia are measured. Behavior is related to the material microstructure and phase assemblage. The stability of the materials is assessed after long-term exposure appropriate for diesel engine application. Properties measured included flexure strength, elastic modulus, fracture toughness, creep, thermal shock, thermal expansion, internal friction, and thermal diffusivity. Stability is assessed by measuring the residual property after 1000 hr/1000C static exposure. Additionally static fatigue and thermal fatigue testing is performed. Both yttria-stabilized and magnesia-stabilized materials are compared and contrasted. The major limitations of these materials are short term loss of properties with increasing temperature as the metastable tetragonal phase becomes more stable. Fine grain yttria-stabilized material (TZP) is higher strength and has a more stable microstructure with respect to overaging phenomena. The long-term limitation of Y-TZP is excessive creep deformation. Magnesia-stabilized PSZ has relatively poor stability at elevated temperature. Overaging, decomposition, and/or destabilization effects are observed. The major limitation of Mg-PSZ is controlling unwanted phase changes at elevated temperature.

Larsen, D. C.↗

NASA NTRS1988

Ceramic Thermal Barriers For Dirty-Fuel Turbines

Report discusses performances of ceramic thermal-barrier coating materials for use in electric-utility gas-turbine engines. Variations of standard coating evaluated in search for coating resistant to dirty fuel. Variations included alterations of level of yttria, replacement of yttria by other stabilizers, controlling surface density (by plasma spray processing, infiltration, laser glazing, or sputtering), and interface treatments.

Miller, Robert A.↗

NASA NTRS1995

Elevated temperature creep properties of NiAl cryomilled with and without Y2O3

The creep properties of lots of NiAl cryomilled with and without Y2O3 have been determined in compression and tension. Although identical cryomilling procedures were used, differences in composition were found between the lot ground with 0.5 vol% yttria and the lot ground without Y2O3. Compression testing between 1000 and 1300 K yielded similar creep strengths for both materials, while tensile creep rupture testing indicated that the yttria-containing alloy was slightly stronger than the Y2O3-free version. Both compression and tensile testing showed two deformation regimes; whereas the stress state did not affect the high stress exponent (n approximately equals 10) mechanism, the low stress exponent regime n was approximately 6 in tension and approximately 2 in compression. The strengths in tension were somewhat less than those measured in compression, but the estimated activation energies (Q) of approximately 600 kJ/mol for tensile testing were closer to the previously measured values (approximately 700 kJ/mol) for NiAl-AlN and very different from the Q's of 400 and 200 kJ/mol for compression tests in the high and low stress exponent regimes, respectively. A Larson-Miller comparison indicated that cryomilling can produce an alloy with long-term, high-temperature strength at least equal to conventional superalloys.

Whittenberger, J. Daniel↗

NASA NTRS1997

Plasma-Sprayed Refractory Oxide Coatings on Silicon-Base Ceramics

Silicon-base ceramics are promising candidate materials for high temperature structural applications such as heat exchangers, gas turbines and advanced internal combustion engines. Composites based on these materials are leading candidates for combustor materials for HSCT gas turbine engines. These materials possess a combination of excellent physical and mechanical properties at high temperatures, for example, high strength, high toughness, high thermal shock resistance, high thermal conductivity, light weight and excellent oxidation resistance. However, environmental durability can be significantly reduced in certain conditions such as when molten salts, H2 or water vapor are present. The oxidation resistance of silicon-base materials is provided by SiO2 protective layer. Molten salt reacts with SiO2 and forms a mixture of SiO2 and liquid silicate at temperatures above 800C. Oxygen diffuses more easily through the chemically altered layer, resulting in a catastrophic degradation of the substrate. SiC and Si3N4 are not stable in pure H2 and decompose to silicon and gaseous species such as CH4, SiH, SiH4, N2, and NH3. Water vapor is known to slightly increase the oxidation rate of SiC and Si3N4. Refractory oxides such as alumina, yttria-stabilized zirconia, yttria and mullite (3Al2O3.2SiO2) possess excellent environmental durability in harsh conditions mentioned above. Therefore, refractory oxide coatings on silicon-base ceramics can substantially improve the environmental durability of these materials by acting as a chemical reaction barrier. These oxide coatings can also serve as a thermal barrier. The purpose of this research program has been to develop refractory oxide chemical/thermal barrier coatings on silicon-base ceramics to provide extended temperature range and lifetime to these materials in harsh environments.

Tewari, Surendra↗

NASA NTRS1993

Characteristics of an Elevated Temperature ALN Particulate Reinforced NiAl

High energy milling of NiAl in liquid nitrogen (cryomilling) leads to the formation of a discontinuously AlN particle reinforced aluminide which has shown good potential as a high strength oxidation resistant material. Experiments have demonstrated that cryomilling is repeatable, and materials with reproducible chemistries and mechanical properties result. Furthermore, it is possible to vary the AlN content through control of the milling parameters. Tensile creep as well as compressive creep testing has been undertaken on a lot of NiAl-AlN. While this material is weaker in tension than compression, the tensile strength is respectable: for example, the creep rupture life exceeds 2700 h at 1300 K, 50 MPa. Heat treatment of the particulate reinforced aluminide at 1600 K promotes AlN growth which weakens the material but does not change the deformation mechanism. Cyclic oxidation testing of lots of NiAl-AlN which were cryomilled with and without yttria reveal that Y2O3 promotes better oxidation resistance. However, the presence or absence of yttria had no affect on the mechanical properties.

Whittenberger, J. D.↗

NASA NTRS1999

Thermal-Mechanical Stability of Single Crystal Oxide Refractive Concentrators for High-Temperature Solar Thermal Propulsion

Single crystal oxides such as yttria-stabilized zirconia (Y2O3-ZrO2), yttrium aluminum garnet (Y3Al5O12, or YAG), magnesium oxide (MgO) and sapphire (Al2O3) are candidate refractive secondary concentrator materials for high temperature solar propulsion applications. However, thermo-mechanical reliability of these components in severe thermal environments during the space mission sun/shade transition is of great concern. Simulated mission tests are important for evaluating these candidate oxide materials under a variety of transient and steady-state heat flux conditions, and thus provide vital information for the component design. In this paper, a controlled heat flux thermal shock test approach is established for the single crystal oxide materials using a 3.0 kW continuous wave CO2 laser, with a wavelength 10.6 micron. Thermal fracture behavior and failure mechanisms of these oxide materials are investigated and critical temperature gradients are determined under various temperature and heating conditions. The test results show that single crystal sapphire is able to sustain the highest temperature gradient and heating-cooling rate, and thus exhibit the best thermal shock resistance, as compared to the yttria-stabilized zirconia, yttrium aluminum garnet, and magnesium oxide.

Zhu, Dongming↗

NASA NTRS1999

Thermal-Mechanical Stability of Single Crystal Oxide Refractive Concentrators for High-Temperature Solar Thermal Propulsion

Zhu, Dongming↗

NASA NTRS1998

Characterization of the Sol-Gel Transition for Zirconia-Toughened Alumina Precursors

High purity ZTA ceramic powders with and without yttria were produced using metal alkoxide precursors. ZTA ceramic powders with varying volume percents of zirconia were prepared (7, 15, and 22%). Aluminum tri-sec butoxide, zirconium propoxide, and yttrium isopropoxide were the reagents used. Synthesis conditions were varied to control the hydrolysis and the aging conditions for the sol to gel transition. FTIR analysis and theological characterization were used to follow the structural evolution during the sol to gel transition. The greater extent of hydrolysis and the build-up of structure measured from viscoelastic properties were consistent. Heat treatment was conducted to produce submicron grain fully crystalline ZTA ceramic powders. In all experimental cases a-alumina and tetragonal zirconia phases were confirmed even in the absence of yttria.

Moeti, I.↗