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At least 109 records · Page 6

Effect of W and WC on the oxidation resistance of yttria-doped silicon nitride

The effect of W and WC contamination on the oxidation and cracking in air of sintered Si3N4 - 8 w/o Y2O3 ceramics at 500, 750, and 1350 C is examined. A mixture of Si3N4 - 8Y2O3, milled with alumina balls, was divided into four portions. Three portions were doped with 2 w/o WC W, and 4 w/o W respectively, in order to simulate contamination during milling. The fourth portion was undoped and used on a control. The addition of W or WC did not affect the phase relationships in the system, as all bars with or without additions contained melilite as the major Si-Y-O-N phase after sintering. At 750 C, instability (rapid oxidation and cracking) of W-doped bars appears to have occurred as a result of oxidation of the tungsten containing melilite phase. No intermediate temperature instability was observed in bars containing 2 w/o WC or in bars with no additive. Specimens exposed at 1350 C had good oxidation resistance due to the formation of a protective siliceous oxide layer. A specimen containing 4 w/o W which was preoxidized at 1350 C had improved oxidation resistance at 750 C. The tendency towards oxidation and cracking of Si3N4 - 8 Y2O3 at 750 C is concluded to be related to tungsten content of the sintered bars.

Schuon, S.↗

Effect of Yttria additives on properties of pressureless-sintered silicon nitride

Si3N4-base ceramics were made from milled Si3N4 containing 11.1 wt% SiO2 and oxide additives by pressureless sintering at 1760 C. The four-point-average moduli of rupture were 460, 515, and 515 MPa at room temperature and 270, 256, and 227 MPa at 1400 C for compositions with 3.67, 7.22, and 14.0 wt% Y2O3, respectively. The oxidation resistance of these compositions decreased with increasing Y2O3 in the 600 to 1400 C range, and no surface oxide cracking or spalling was noted. Partial substitution of Al2O3 for Y2O3 reduced both strength and oxidation resistance.

Arias, A.↗

Neutron and X-ray diffraction of plasma-sprayed zirconia-yttria thermal barrier coatings

ZrO2-7.8mol. pct. YO1.5, a fused powder, and ZrO2-8.7mol. pct. YO1.5, a prereacted powder, were plasma-sprayed onto steel substrates. Neutron diffraction and X-ray diffraction of the as-received powder, the powder plasma sprayed into water, as-sprayed coatings, and coatings heat-treated for 10 and 100 h were carried out to study phase transformations and ordering of the oxygen ions on the oxygen sublattice. The as-received fused powder has a much lower monoclinic percentage than does the pre-reacted powder, this resulting in a much lower monoclinic percentage in the coating. Heat treatment increases the percentages of the cubic and monoclinic phases, while decreasing the tetragonal content. An ordered tetragonal phase is detected by the presence of extra neutron diffraction peaks. These phase transformations and ordering will result in volume changes. The implications of these transformations on the performance of partially stabilized zirconia thermal barrier coatings is discussed.

Shankar, N. R.↗

Destabilization of yttria-stabilized zirconia induced by molten sodium vanadate-sodium sulfate melts

The extent of surface destabilization of ZrO2 - 8 wt percent Y2O3 ceramic disks was determined after exposure to molten salt mixtures of sodium sulfate containing up to 15 mole percent sodium metavanadate (NaVO3) at 1173 K. The ceramic surface was observed to transform from the cubic/tetragonal to monoclinic phase, concurrent with chemical changes in the molten salt layer in contact with the ceramic. Significant attack rates were observed in both pure sulfate and metavanadate sulfate melts. The rate of attack was found to be quite sensitive to the mole fraction of vanadate in the molten salt solution and the partial pressure of sulfur trioxide in equilibrium with the salt melt. The observed parabolic rate of attack is interpreted to be caused by a reaction controlled by diffusion in the salt that penetrates into the porous layer formed by the destabilization. The parabolic rate constant in mixed sodium metavanadate - sodium sulfate melts was found to be proportional to the SO3 partial pressure and the square of the metavanadate concentration. In-situ Raman spectroscopic measurements allowed simultaneous observations of the ceramic phases and salt chemistry during the attack process.

Nagelberg, A. S.↗

Temperature dependence of hardness in yttria-stabilized zirconia single crystals

The temperature dependence of hardness and microcracking in single-crystal 9.5-mol pct-Y2O3-fully-stabilized cubic-ZrO2 was studied as a function of orientation. Crack lengths increased with increased temperature up to 500 C; above 800 C, no cracks were found, indicating an indentation brittle-to-ductile transition of about 800 C. The temperature dependence of hardness was reduced around 500 C. Etching studies to delineate the plastic zone around and below indents identified the operative slip systems. The role of dislocations and their interactions within the plastic zone on the hardness and indentation fracture behavior of cubic-ZrO2 are discussed.

Morscher, Gregory N.↗

Factors Influencing Residual Stresses in Yttria Stabilized Zirconia Thermal Barrier Coatings

To improve gas turbine and diesel engine performance using thermal barrier coatings (TBC's) requires an understanding of the factors that influence the in-service behavior of thermal barrier coatings. One of the many factors related to coating performance is the state of stress in the coating. The total stress state is composed of the stresses due to the in-service loading history and the residual stresses. Residual stresses have been shown to affect TBC life, the bond strength of thermal spray coatings, and the fatigue life of tungsten carbide coatings. Residual stresses are first introduced in TBC's by the spraying process due to elevated temperatures during processing and the difference in coefficients of thermal expansion of the top coat, bond coat, and substrate. Later, the residual stresses can be changed by the in-service temperature history due to a number of time and temperature dependent mechanisms, such as oxidation, creep, and sintering. Silica content has also been shown to affect sintering and the cyclic life of thermal barrier coatings. Thus, it is important to understand how the spraying process, the in-service thermal cycles, and the silica content can create and alter residual stresses in thermal barrier coatings.

McGrann, Roy T. R.↗

Advanced Multi-Component Defect Cluster Oxide Doped Zirconia-Yttria Thermal Barrier Coatings

The advantages of using ceramic thermal barrier coatings in gas turbine engine hot sections include increased fuel efficiency and improved engine reliability. However, current thermal barrier coatings will not have the low thermal conductivity and necessary sintering resistance under higher operating temperatures and thermal gradients required by future advanced ultra efficient and low emission aircraft engines. In this paper, a novel oxide defect cluster design approach is described for achieving low thermal conductivity and excellent thermal stability of the thermal barrier coating systems. This approach utilizes multi-component rare earth and other metal cluster oxide dopants that are incorporated in the zirconia-yttna based systems, thus significantly reducing coating thermal conductivity and sintering resistance by effectively promoting the formation of thermodynamically stable, essentially immobile defect clusters and/or nanoscale phases. The performance of selected plasma-sprayed cluster oxide thermal barrier coating systems has been evaluated. The advanced multi-component thermal barrier coating systems were found to have significantly lower initial and long-term thermal conductivities, and better high temperature stability. The effect of oxide cluster dopants on coating thermal conductivity, sintering resistance, oxide grain growth behavior and durability will be discussed.

Zhu, Dongming↗

Advanced thermal barrier coating systems

Current state-of-the-art thermal barrier coating (TBC) systems consist of partially stabilized zirconia coatings plasma sprayed over a MCrAlY bond coat. Although these systems have excellent thermal shock properties, they have shown themselves to be deficient for a number of diesel and aircraft applications. Two ternary ceramic plasma coatings are discussed with respect to their possible use in TBC systems. Zirconia-ceria-yttria (ZCY) coatings were developed with low thermal conductivities, good thermal shock resistance and improved resistance to vanadium containing environments, when compared to the baseline yttria stabilized zirconia (YSZ) coatings. In addition, dense zirconia-titania-yttria (ZTY) coatings were developed with particle erosion resistance exceeding conventional stabilized zirconia coatings. Both coatings were evaluated in conjunction with a NiCr-Al-Co-Y2O3 bond coat. Also, multilayer or hybrid coatings consisting of the bond coat with subsequent coatings of zirconia-ceria-yttria and zirconia-titania-yttria were evaluated. These coatings combine the enhanced performance characteristics of ZCY with the improved erosion resistance of ZTY coatings. Improvement in the erosion resistance of the TBC system should result in a more consistent delta T gradient during service. Economically, this may also translate into increased component life simply because the coating lasts longer.

Dorfman, M. R.↗

Comparative study of three yttrium organometallic compounds for the stabilization of the cubic phase in YSZ deposited by PE-CVD

In this work, the efficiencies of three organometallic yttrium precursors used to produce YSZ coatings by plasma-enhanced chemical vapor deposition were studied. Yttrium (III) acetylacetonate, Y (acac) 3 , yttrium (III) hexafluoroacetylacetonate, Y (acacF 6 ) 3 , and yttrium (III) tris(2,2,6,6-tetramethyl-3,5-heptanedionate), Y (tmhd) 3 , were used to stabilize the cubic phase in zirconia deposited at temperatures from 500 to 800 °C. Our results showed that at temperatures between 500 and 600 °C, Y (tmhd) 3 appeared to be the most efficient dopant as it introduced the highest concentration of yttria (1–2.7 mol%) with only 6.4–5.6 at.% carbon. However, at 700 and 800 °C, Y (acac) 3 introduced twice as much yttria (8–15 mol%) as Y (tmhd) 3 with almost the same amount of carbon (5.4–3 at.%). Conversely, Y (acacF6)3 was the least efficient as it maintained a low concentration of yttria of around 0.7–1.8 mol% with 3.6–8.2 at.% carbon for all the deposition temperatures. Among these precursors, only Y (acac) 3 surpassed 8 mol% yttria and achieved a fully stabilized cubic phase at 800 °C, with the remaining samples stabilizing only the tetragonal phase. The tetragonal phase was stabilized due to the formation of crystallites of around 10 nm. The observed difference in the efficiency of the three precursors was correlated to important differences in their decomposition behavior as observed by mass spectrometry and thermogravimetry/differential scanning calorimetry.

36 MATERIALS SCIENCE↗

Compatibility experiments of facilities, materials, and propellants for electrothermal thrusters

Experiments were performed to determine the compatibility of materials and propellants for electro-thermal thrusters. Candidate propellants for resistojet propulsion include carbon dioxide, methane, hydrogen, ammonia, and hydrazine. The materials being examined are grain stabilized platinum for resistojets for Space station and rhenium for high performance resistojets for satellites. Heater mass loss and deterioration of materials were evaluated. A coiled tube of platinum, with yttria dispersed throughout the base material to inhibit grain growth, was tested in carbon dioxide at 1300 C for 2000 hr. Post-test examination indicated the platinum-yttria heater would last over 100 000 hr with less than 10 percent mass loss. Short-term compatibility tests were conducted to test the integrity of the platinum-yttria in hydrogen, methane, carbon dioxide/methane mixtures and ammonia environments. In each of these 100 hr tests, the platinum-yttria mass change indicated a minimum coil life of 100 000 hr. Facility related effects were investigated in materials tests using rhenium heated to high tempertures. Vacuum facility water reduction was monitored using a mass spectrometer. In vacuum environments obtained using only diffusion pumping and those obtained with the assistance of cryogenic equipment there were mass gains in the rhenium heaters. These mass gains were the result of the high amount of oxygen and water contained in the gas. Propellant purity and preferred test facility environments are discussed.

Whalen, M. V.↗

Compatibility experiments of facilities, materials, and propellants for electrothermal thrusters

Experiments were performed to determine the compatibility of materials and propellants for electro-thermal thrusters. Candidate propellants for resistojet propulsion include carbon dioxide, methane, hydrogen, ammonia, and hydrazine. The materials being examined are grain stabilized platinum for resistojets for space station and rhenium for high performance resistojets for satellites. Heater mass loss and deterioration of materials were evaluated. A coiled tube of platinum, with yttria dispersed throughout the base material to inhibit grain growth, was tested in carbon dioxide at 1300 C for 2000 hr. Post-test examination indicated the platinum-yttria heater would last over 100,000 hr with less than 10 percent mass loss. Short-term compatibility tests were conducted to test the integrity of the platinum-yttria in hydrogen, methane, carbon dioxide/methane mixtures and ammonia environments. In each of these 100 hr tests, the platinum-yttria mass change indicated a minimum coil life of 100,000 hr. Facility related effects were investigated in materials tests using rhenium heated to high temperatures. Vacuum facility water reduction was monitored using a mass spectrometer. In vacuum environments obtained using only diffusion pumping and those obtained with the assistance of cryogenic equipment there were mass gains in the rhenium heaters. These mass gains were the result of the high amount of oxygen and water contained in the gas. Propellant purity and preferred test facility environments are discussed.

Whalen, M. V.↗

Development of Ceramic Solid-State Laser Host Material

Polycrystalline ceramic laser materials are gaining importance in the development of novel diode-pumped solid-state lasers. Compared to single-crystals, ceramic laser materials offer advantages in terms of ease of fabrication, shape, size, and control of dopant concentrations. Recently, we have developed Neodymium doped Yttria (Nd:Y2O3) as a solid-state ceramic laser material. A scalable production method was utilized to make spherical non agglomerated and monodisperse metastable ceramic powders of compositions that were used to fabricate polycrystalline ceramic material components. This processing technique allowed for higher doping concentrations without the segregation problems that are normally encountered in single crystalline growth. We have successfully fabricated undoped and Neodymium doped Yttria material up to 2" in diameter, Ytterbium doped Yttria, and erbium doped Yttria. We are also in the process of developing other sesquioxides such as scandium Oxide (Sc2O3) and Lutesium Oxide (Lu2O3) doped with Ytterbium, erbium and thulium dopants. In this paper, we present our initial results on the material, optical, and spectroscopic properties of the doped and undoped sesquioxide materials. Polycrystalline ceramic lasers have enormous potential applications including remote sensing, chem.-bio detection, and space exploration research. It is also potentially much less expensive to produce ceramic laser materials compared to their single crystalline counterparts because of the shorter fabrication time and the potential for mass production in large sizes.

Prasad, Narasimha S.↗

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.↗

The Detection of Monoclinic Zirconia and Non-Uniform 3D Crystallographic Strain in a Re-Oxidized Ni-YSZ Solid Oxide Fuel Cell Anode

The solid oxide fuel cell (SOFC) anode is often composed of nickel (Ni) and yttria-stabilized zirconia (YSZ). The yttria is added in small quantities (e.g., 8 mol %) to maintain the crystallographic structure throughout the operating temperatures (e.g., room-temperature to >800 °C). The YSZ skeleton provides a constraining structural support that inhibits degradation mechanisms such as Ni agglomeration and thermal expansion miss-match between the anode and electrolyte layers. Within this structure, the Ni is deposited in the oxide form and then reduced during start-up; however, exposure to oxygen (e.g., during gasket failure) readily re-oxidizes the Ni back to NiO, impeding electrochemical performance and introducing complex structural stresses. In this work, we correlate lab-based X-ray computed tomography using zone plate focusing optics, with X-ray synchrotron diffraction computed tomography to explore the crystal structure of a partially re-oxidized Ni/NiO-YSZ electrode. These state-of-the-art techniques expose several novel findings: non-isotropic YSZ lattice distributions; the presence of monoclinic zirconia around the oxidation boundary; and metallic strain complications in the presence of variable yttria content. This work provides evidence that the reduction–oxidation processes may destabilize the YSZ structure, producing monoclinic zirconia and microscopic YSZ strain, which has implications upon the electrode’s mechanical integrity and thus lifetime of the SOFC.

25 ENERGY STORAGE↗

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.↗