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At least 127 records · Page 7

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.↗

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↗

Enhancing the efficiency benefit of thermal barrier coatings for homogeneous charge compression ignition engines through application of a low-k oxide

Prior experiments reported by the authors have proven the hypothesis that achieving a dynamic temperature swing on the combustion chamber surface will lead to improved thermal and combustion efficiencies of the homogeneous charge compression ignition engine. A thin layer of yttria-stabilized zirconia, roughly 150 μm, was plasma sprayed on the piston top. It led to markedly advanced ignition and heat release in the gasoline homogeneous charge compression ignition engine, accompanied with reduced unburnt hydrocarbon and carbon monoxide emissions, improved combustion efficiency, and a higher thermal efficiency. A related computational study highlighted the critical role of coating thermal conductivity in achieving a desired dynamic response; hence, the second phase of experimental investigations focused on introducing structured porosity in the yttria-stabilized zirconia coating, as a means of reducing effective conductivity. Indeed, additional incremental improvements were observed, as well as limitations related to adverse effects of the surface roughness and the fuel interactions with the surface roughness and open pores. Erosion can also be a problem in a direct injection engine. Therefore, the third round of investigations focused on a material with a natively low conductivity (low-k), sprayed on the top of an Al piston in a relatively dense form, and in a way that yields a smooth surface. The objective was to capitalize on the low conductivity, while avoiding the pitfalls accompanying high-porosity formulations. The heat-storage capacity was limited by keeping the thickness relatively low. The results verify the paramount importance of thermal conductivity in the context of high “temperature swing” behavior and indicate a potential to improve the homogeneous charge compression ignition engine’s combustion efficiency roughly 1.5%, with the overall indicated efficiency improvement on the order of 5%, on a relative basis. In addition, the low-k oxide thermal barrier applied to the piston extended significantly the low-load homogeneous charge compression ignition operability limit.

42 ENGINEERING↗

Nanostructured Oxide-Dispersion-Strengthened CoCrFeMnNi High-Entropy Alloys with High Thermal Stability

A nanostructured oxide-dispersion-strengthened (ODS) CoCrFeMnNi high-entropy alloy (HEA) is synthesized by a powder metallurgy process. The thermal stability, including the grain size and crystal structure of the HEA matrix and oxide dispersions, is carefully investigated by X-ray diffraction (XRD) and electron microscopy characterizations after annealing at 900 °C. The limited grain growth may be attributed to Zener pinning of yttria dispersions that impede the grain boundary mobility and diffusivity. The high hardness is caused by both the fine grain size and yttria dispersions, which are also retained after annealing at 900 °C. In this study, it is implied that the combination of ODS and HEA concepts may provide a new design strategy for the development of thermally stable nanostructured alloys for extreme environments.

36 MATERIALS SCIENCE↗

Dispersal of high-burnup fuel fragment surrogate particles during and after loss-of-coolant accident tests

The issue of fuel fragmentation, relocation, and dispersal is critical in the licensing and use of high-burnup (>62 GWd/MTU) nuclear fuel in light water reactors (LWRs). In this work, two test series are reported that examine the fragment dispersal during a burst event and an additional dispersal following the burst due to vibrations in the rod, such as those induced by accident recovery systems. To examine dispersal during the balloon and burst portion of a Loss-of-Coolant Accident event, HfO 2 fragments and yttria-stabilized zirconia pellets were filled into an as-fabricated cladding tube, which was then pressurized and subjected to loss-of-coolant accident testing in steam. Results from this test were found to be highly non-prototypic, and dispersal was both significantly more violent and significantly greater in magnitude than identified for actual fuel tests. These findings were attributed to the conservative (more dispersive) nature of the particles chosen for dispersal and to the details of the test conditions used that led to particularly wide bursts. Further, the second set of tests examined dispersal following the burst when vibrations were induced in the rod, primarily via recovery activities such as Emergency Core Cooling System actuation leading to rapid water addition. Post-burst dispersal testing was performed by inducing sinusoidal oscillations with 2–25 nm peak-to-peak amplitude and 2–5 Hz frequencies in pre-burst rods that had been refilled with HfO 2 fragments or high-burnup fragment surrogate mixture of HfO 2 fragments and yttria-stabilized zirconia sands. Testing revealed that rods with large burst openings (7 mm wide in this work) led to unmitigated dispersal from above the burst zone but that smaller bursts (5 mm wide), although still much larger than the mean fragment size of 3 mm, led to effectively no dispersal because of interparticle locking. Additionally, mixture and moisture were found to impact the amount of dispersal: mixtures increased dispersal, and moisture drastically reduced it. The implications of these findings on likely dispersal from actual fuel are discussed.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Impact of Sr-Containing Secondary Phases on Oxide Conductivity in Solid-Oxide Electrolyzer Cells

Solid-oxide electrolyzer cells (SOECs) based on a yttria-stabilized zirconia (YSZ) oxide electrolyte produce hydrogen from water with the assistance of excess thermal energy; however, Sr diffusion within the Gd-doped CeO 2 (GDC) barrier layer during processing or operation can lead to the formation of unwanted secondary phases such as SrO and SrZrO 3 . Here, to establish and compare the degree of impact of these phases on SOEC performance, we conduct first-principles calculations to study their bulk oxide conductivities and compare them to that of the YSZ electrolyte. We find that SrO has a low conductivity arising from the poor mobility and low concentration of mobile oxygen vacancies, and its presence in SOECs should therefore be avoided. SrZrO 3 also has a lower oxide conductivity than YSZ; however, this discrepancy is primarily due to lower vacancy concentrations rather than low mobility. We find that sufficient levels of Y-doping on the Zr site can increase oxygen vacancy concentrations in SrZrO 3 to achieve an oxide ionic conductivity on par with that of YSZ, thereby mitigating any potential deleterious effect on transport performance. Energy-dispersive X-ray spectroscopy confirms that Y is the most common minority element present in SrZrO 3 forming near the GDC–YSZ interface, alleviating concerns regarding the impact of SrZrO 3 on device performance. These results from our combined computational–experimental analysis can inform future engineering strategies designed to limit the detrimental effects of Sr-induced secondary phase formation on SOEC performance.

08 HYDROGEN↗

Siloxane Deposition on the Ni-YSZ Solid Oxide Fuel Cell Anode Exposed to Bio-Syngas

Siloxane, a common contaminant present in biogas, is known for adverse effects on cogeneration prime movers. In this study, the siloxane deposition products and mechanism in the solid oxide fuel cell nickel-yttria stabilized zirconia (Ni-YSZ) anode are investigated analytically and experimentally. An SOFC with Ni-YSZ anode and pure Ni/YSZ pellets were exposed to a simulated biogas-reformate fuel with octamethylcyclotetrasiloxane (D4) contamination at 750 °C. The electrochemical characterization results show that the SOFCs performance degradation caused by D4 contamination is irreversible. Morphology and XRD results illustrate that silicon and carbon deposition can both be detected in the anode and pellets. Graphite, SiC and SiO2 are all possible products based on the results of XRD test. Here, according to the formation of graphite and SiC, the new mechanism suggests that carbon is also an essential factor in siloxane contamination of Ni-YSZ anodes besides silicon, which can be explained by the catalytic and electrochemical analysis.

25 ENERGY STORAGE↗

An Investigation of the Electrochemical Activity of (Ba/Sr)FeO 3-y Anodes

FeO x , SrFeO 3-y (SF), and Ba 0.5 Sr 0.5 FeO 3–y (BSF) were studied for application as fuel oxidation catalysts in solid oxide fuel cells (SOFC) anodes. Electrodes were prepared by impregnation into porous yttria-stabilized zirconia (YSZ), with La 0.3 Sr 0.7 TiO 3–y (LST) added for electronic conductivity. The electrode impedances decreased dramatically upon addition of SF and BSF and much less when only SrO or FeO x were added. Temperature Programmed Desorption (TPD) of O 2 from oxidized BSF showed O 2 desorbing between 200 °C and 700 °C, while no O 2 desorbed from Fe 2 O 3 below 900 °C. The results, together with thermodynamic analysis, suggest that stabilization of Fe +4 in the perovskite lattice plays an important role in enhancing the catalytic activity of SF and BSF by providing access to a Fe 3+ /Fe 4+ redox couple that can accept oxygen anions from the yttria-stabilized zirconia (YSZ) electrolyte. Oxygen is weakly bound to these sites facilitating its reaction with adsorbed H 2 .

Electrochemistry↗

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.↗

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.↗

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.↗

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.↗

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.↗

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.↗

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.↗

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.↗

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↗