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At least 55 records · Page 3

Sintering and Creep Behavior of Plasma-Sprayed Zirconia and Hafnia Based Thermal Barrier Coatings

The sintering and creep of plasma-sprayed ceramic thermal barrier coatings under high temperature conditions are complex phenomena. Changes in thermomechanical and thermophysical properties and in the stress response of these coating systems as a result of the sintering and creep processes are detrimental to coating thermal fatigue resistance and performance. In this paper, the sintering characteristics of ZrO2-8wt%y2O3, ZrO2-25wt%CeO2-2.5wt%Y2O3, ZrO2-6w%NiO- 9wt%Y2O3, ZrO2-6wt%Sc2O3-2wt%y2O3 and HfO2-27wt%y2O3 coating materials were investigated using dilatometry. It was found that the HfO2-Y2O3 and baseline ZrO2-Y2O3 exhibited the best sintering resistance, while the NiO-doped ZrO2-Y2O3 showed the highest shrinkage strain rates during the tests. Higher shrinkage strain rates of the coating materials were also observed when the specimens were tested in Ar+5%H2 as compared to in air. This phenomenon was attributed to an enhanced metal cation interstitial diffusion mechanism under the reducing conditions. It is proposed that increased chemical stability of coating materials will improve the material sintering resistance.

Zhu, Dongming↗

Low-cycle fatigue of thermal-barrier coatings at 982 deg C

The low-cycle fatigue lives of ZrO2-NiCrAlY and Al2O3-ZrO2-NiCrAlY thermal-barrier coatings in air at 982 C were determined from cyclic flexural tests of coated TAZ-8A strips. Strains were computed as a function of specimen displacements from a nonlinear, three-dimensional stress analysis program. Fatigue resistances of thermal-barrier coatings applied to the strips were compared with those of uncoated and NiCrAlY-coated strips. The results indicate that ZrO2 is about four times greater in fatigue life than TAZ-8A at 982 C, that ZrO2 would probably retain that fatigue strength up to 1316 C, and that adding an outer coat of Al2O3 to ZrO2 is neither beneficial nor detrimental to fatigue resistance.

Kaufman, A.↗

Morphological Evolution and Weak Interface Development within CVD-Zirconia Coating Deposited on Hi-Nicalon Fiber

The phase contents and morphology of a ZrO2 fiber coating deposited at 1050 C on Hi-Nicalon(Tm) by chemical vapor deposition were examined as a function of deposition time from 5 to 120 min. The morphological evolution in the ZrO2 coating was correlated to the development of delamination within the ZrO2 coating. The delamination appears to occur as a result of: (1) continuous formation of tetragonal ZrO2 nuclei on the deposition surface; (2) martensitic transformation of the tetragonal phase to a monoclinic phase upon reaching a critical grain size; and (3) development of significant compressive hoop stresses due to the volume dilation associated with the transformation. Our observations suggest that it will be of critical importance to further understand and eventually control the nucleation and grain growth behavior of CVD ZrO2 and its phase transformation behavior for its potential applications for composites.

Li, Hao↗

Preliminary study of cyclic thermal shock resistance of plasma-sprayed zirconium oxide turbine outer air seal shrouds

Several experimental concepts representing potential high pressure turbine seal material systems were subjected to cyclic thermal shock exposures similar to those that might be encountered under severe engine start-up and shut-down sequences. All of the experimental concepts consisted of plasma-sprayed yttria stabilized ZrO2 on the high temperature side of the blade tip seal shroud. Between the ZrO2 and a cooled, dense metal backing, various intermediate layer concepts intended to mitigate thermal stresses were incorporated. Performance was judged on the basis of the number of thermal shock cycles required to cause loss of seal material through spallation. The most effective approach was to include a low modulus, sintered metal pad between the ZrO2 and the metallic backing. It was also found that reducing the density of the ZrO2 layer significantly improved the performance of specimens with plasma-sprayed metal/ceramic composite intermediate layers.

Bill, R. C.↗

Improved performance of silicon nitride-based high temperature ceramics

Results are presented regarding experiments intended for improving the strength and toughness of hot-pressed Si3N4 (HPSN), improving the strength and oxidation resistance of reaction-sintered Si3N4 (RSSN), and improving the strength and oxidation resistance of sinterable Si-Al-O-N compositions. It is shown that the use of ZrO2 instead of MgO as a sintering aid improved the room-temperature and high-temperature flexural strength of HPSN, in addition to enhancing the rupture strength and Charpy impact resistance. The use of crushable energy absorbing layers increased the impact resistance of HPSN. Impregnation of RSSN with solutions that oxidize to Al2O3 or ZrO2 resulted in increased bending strength at room temperature. Beta-prime Si-Al-O-N sintered to full density by means of the sintering aids CeO2, Y2O3, and ZrO2 yielded the greatest strength with Y2O3 and the greatest oxidation resistance with ZrO2.

Ashbrook, R. L.↗

Thermal barrier coatings for superalloys

The current status of ceramic thermal barrier coatings for protection of turbine airfoil components is reviewed. Test results for an early duplex coating system ZrO2-12% Y2O3/Ni-16% Cr-6% Al-0.6% Y, improved system ZrO2-8% Y2O3/Ni-17% Cr-5% Al-0.35% Y, and air/fuel impurity tolerant systems based on ZrO2-8% Y2O3, 2CaO-SiO2, and a MgO-NiCrAlY cermet are discussed. Preliminary test results at 800 C for a graded ZrO2-8% Y2O3/Ni-20% Cr-11% Al-0.4% Y coating system show that the coating can survive at least 500 hr in the presence of 50 ppm V plus other fuel contaminants and additives.

Miller, R. A.↗

Microstructural aspects of zirconia thermal barrier coatings

Various combination of plasma-sprayed bond coatings and zirconia ceramic coatings on a nickel-based superalloy substrate were tested by static thermal exposure at 1200 C and cyclic thermal exposure to 1000 C. The bond coats were based on Ni-Cr-Al alloys with additions of rare earth elements and Si. The ceramic coats were various ZrO2-Y2O3 compositions, of which the optimum was found to be ZrO2-8.9 wt percent Y2O3. Microstructural analysis showed that resistance to cracking during thermal exposure is strongly related to deleterious phase changes. Zones depleted of Al formed at the bond coat/ceramic coat interface due to oxidation and at the bond coat/substrate interface due to interdiffusion, leading eventually to breakdown of the bond coat. The 8.9 percent Y2O3 coating performed best because the as-sprayed metastable tetragonal phase converted slowly into the low-Y2O3 tetragonal plus high-Y2O3 cubic-phase mixture, so that the deleterious monoclinic phase was inhibited from forming. Failure appeared to start with the formation of circumferential cracks in the zirconia, probably due to compressive stresses during cooling, followed by the formation of radial cracks due to tensile stresses during heating. Cracks appeared to initiate at the Al2O3 scale/bond coat interface and propagate through the zirconia coating. Comparisons were made with the behavior of bulk ZrO2-Y2O3 and the relationship between the microstructure of the tetragonal phase and the phase diagram. A separate investigation was also made of the ZrO2-Al2O3 interface.

Mitchell, T. E.↗

Thermal modelling of various thermal barrier coatings in a high heat flux rocket engine

Traditional Air Plasma Sprayed (APS) ZrO2-Y2O3 Thermal Barrier Coatings (TBC's) and Low Pressure Plasma Sprayed (LPPS) ZrO2-Y2O3/Ni-Cr-Al-Y cermet coatings were tested in a H2/O2 rocked engine. The traditional ZrO2-Y2O3 (TBC's) showed considerable metal temperature reductions during testing in the hydrogen-rich environment. A thermal model was developed to predict the thermal response of the tubes with the various coatings. Good agreement was observed between predicted temperatures and measured temperatures at the inner wall of the tube and in the metal near the coating/metal interface. The thermal model was also used to examine the effect of the differences in the reported values of the thermal conductivity of plasma sprayed ZrO2-Y2O3 ceramic coatings, the effect of 100 micron (0.004 in.) thick metallic bond coat, the effect of tangential heat transfer around the tube, and the effect or radiation from the surface of the ceramic coating. It was shown that for the short duration testing in the rocket engine, the most important of these considerations was the effect of the uncertainty in the thermal conductivity of temperatures (greater than 100 C) predicted in the tube. The thermal model was also used to predict the thermal response of the coated rod in order to quantify the difference in the metal temperatures between the two substrate geometries and to explain the previously-observed increased life of coatings on rods over that on tubes. A thermal model was also developed to predict heat transfer to the leading edge of High Pressure Fuel Turbopump (HPFTP) blades during start-up of the space shuttle main engines. The ability of various TBC's to reduce metal temperatures during the two thermal excursions occurring on start-up was predicted. Temperature reductions of 150 to 470 C were predicted for 165 micron (0.0065 in.) coatings for the greater of the two thermal excursions.

Nesbitt, James A.↗

Zircon, Baddeleyite, and Reidite Found in Ries Crater Suevite

Introduction: Impact events can generate superheated impact melts and even vapor [1]. In the past decade, evidence of the high temperatures and high pressures of the impact process has been found in the impact melt from terrestrial craters (e.g., Mistastin Lake [2], Meteor Crater [3]) and even on the Moon [4–5]. Often, these studies involve zircon or zirconium-bearing phases. Zircon is a particularly useful mineral, due to its robustness and durability against weathering. It is used principally for chronology, but it has a multitude of geologic applications, including geothermometry and fingerprinting magma sources. Here we focus on its capability of recording impact conditions. Grains of zircon (ZrSiO4) are converted at high temperature and/or pressure during an impact event to reidite (a high-pressure polymorph of ZrSiO4) or to tetragonal-ZrO2 + SiO2 [6]. Reidite and tertragonal-ZrO2 leave identifying relicts in the rocks, markers of the high pressures and/or temperatures these rocks underwent. Ries Crater is a 26-km-diameter peak ring crater in southern Germany that formed approximately 15 Ma [7–9]. Ries is the type locality of the polymict impact breccia known as suevite. Here, we report a microanalytical study of suevite from the Ries impact structure. These analyses are used to inform our understanding of the pressure and temperature conditions involved in creating a polymict impact breccia such as suevite in a peak ring crater. Sample Description: The sample, denoted 16RS08, originates from Otting Quarry, at 48.8777° N, 10.7921° E, approximately 17 km from the center of the Ries Crater in Germany (approximately 4 km outside the crater rim). The material recorded in sample 16RS08 is therefore considered an outer suevite. The outer suevite is a discontinuous layer of polymict impact breccia that occurs outside the central ring of Ries, up to 22 km from the center of the crater [9]. Lithic clasts in the outer suevite consist primarily of crystalline basement rocks (gneiss, granite, amphibolite), with less than 5% of lithic clasts being overlying sedimentary rocks (limestone, sandstone, shale) [9]. The thin section studied contains variably shocked lithic and mineral clasts, impact glass, and interstitial minerals that make up the matrix of the breccia (Fig. 1) [9]. Methods: We used a Cameca SX100 electron probe microanalyzer (EPMA) located in the Kuiper Materials Imaging and Characterization Facility (KMICF) at the University of Arizona to obtain 15 elemental X-ray maps of 16RS08. We next used the JEOL 7900F SEM at the Astromaterials Research & Exploration Science (ARES) at NASA Johnson Space Center (JSC) to obtain electron backscatter diffraction (EBSD) maps and energy dispersive X-ray spectroscopy (EDS) maps of select portions of the section. The EBSD data were collected under beam conditions of 20 kV, and ~9 μA, with step sizes varying from 0.05 to 2 μm. Following EBSD data collection, we processed the data using AZtecCrystal and MTEX, a free MATLAB toolbox. Results: We used the elemental X-ray maps to identify the areas of interest in the section, particularly phosphates and Zr-bearing grains. These areas of interest were then targeted for follow up EBSD and EDS analyses. We have identified, through combined EBSD and EDS analysis, the presence of zircon, reidite, and monoclinic-ZrO2 (baddeleyite) in 16RS08. In 16RS08, we have found singular grains of zircon, zircon with a vermicular baddeleyite halo (Fig. 2a), and granular zircon with reidite (Fig. 2b). The different Zr-rich phases and their corresponding textures signifies that this sample underwent a broad spectrum of pressure and temperature conditions during the impact event. For example, zircons surrounded by a vermicular baddeleyite and SiO2 intergrowth (i.e., Fig. 2a) have been shown to preserve evidence of the extremely high temperatures of impact melt, upwards of 2370 °C [2, 6]. Similarly, reidite and granular zircon (i.e., Fig. 2b) have been shown to preserve evidence of high pressure, as the transition to reidite occurs >30 GPa [3, 6]. Future Work: Next, we will process the EBSD and EDS data for these Zr-rich grains, specifically looking for indicators of cubic- or tetragonal-ZrO2 in the baddeleyite remnants and of shock-precursors to the reidite. To further inform our work, we will also obtain BSE images of these grains using a Hitachi S-4800 SEM in KMICF at the University of Arizona, as well as geochemical spot analyses via EPMA. The data collected will be used to constrain the formation conditions of the Ries Crater outer suevite. Acknowledgments: We thank Ken Domanik and Jerry Chang for their support with data collection. This work was supported by a University of Arizona RII Core Facilities Pilot Program grant and start-up funds to JJB. TME thanks A. Cavosie and N. Timms for assistance during field sampling. We acknowledge support from NASA’s Planetary Science Research program for analysis performed at JSC. References: [1] Melosh H. J. (1989) Oxf. U. Press. [2] Timms et al. (2017) EPSL 477, 52–58. [3] Cavosie et al. (2016) Geology 44:9, 703–706. [4] White et al. (2020) Nature Astr. 4, 974–978. [5] Crow C. A. et al. (2017) GCA 202, 264–284. [6] Timms et al. (2017) Earth-Sci. Rev. 165, 185–202. [7] Schmieder M. et al. (2018) GCA 220, 146–157. [8] Schwarz W. H. et al. (2020) M&PS 55:2, 312–325. [9] Stöffler et al. (2013) M&PS 43:4, 515–589.

Zircon↗

Development and fabrication of insulator seals for thermionic diodes

Eight different types of cermet seals for thermionic diodes were investigated: (1) 1 micron Al2O3 with Nb spheres; (2) 200 A Al2O3 with Nb spheres; (3) 1 micron Al2O3 with Nb 1% Zr spheres; (4) 200 A Al2O3 with Nb 1% Zr spheres; (5) Pure Y2O3 with Nb 1% Zr spheres; (6) Y2O3 3% ZrO2 with Nb 1% Zr spheres; (7) Y2O3 10% ZrO2 with Nb 1% Zr spheres; and (8) ZrO2 12% Y2O3 with Nb 1% Zr spheres. Investigations were made to determine the most favorable fabrication techniques and the effect of the bonding cycle, (length of bonding time and shutdown sequences). The analysis of the seals included tensile test, vacuum test, electrical test and metallurgical examination. At the conclusion of the development phase, 36 seals were fabricated for delivery for evaluation.

Poirier, V. L.↗

Carbon dioxide electrolysis using a ceramic electrolyte

This paper discusses the results of an experimental study of the electrical aspects of carbon dioxide electrolysis using a ceramic electrolyte. The electrolyte compositions used in this study are 8% Y2O3 stabilized ZrO2, 7.5% CaO stabilized ZrO2, and 5% Y2O3 stabilized ThO2. Results indicate that the 8% Y2O3 stabilized ZrO2 is the best material to use for electrolysis, in terms of current as a function of voltage and temperature, and in terms of efficiency of oxide ion flow through it. The poorest results were obtained with the 5% Y2O3 stabilized ThO2 composition. An electrolysis system which might be employed to reclaim oxygen and carbon from effluents of space manufacturing, assuming that an industry would have to electrolyze 258,000 tonnes of CO2 per year, is predicted to require a total cell area of 110,000 sq m of 1 mm thickness and electrical capacity of 441 MW.

Erstfeld, T. E.↗

Creep of plasma sprayed zirconia

Specimens of plasma-sprayed zirconia thermal barrier coatings with three different porosities and different initial particle sizes were deformed in compression at initial loads of 1000, 2000, and 3500 psi and temperatures of 1100 C, 1250 C, and 1400 C. The coatings were stabilized with lime, magnesia, and two different concentrations of yttria. Creep began as soon as the load was applied and continued at a constantly decreasing rate until the load was removed. Temperature and stabilization had a pronounced effect on creep rate. The creep rate for 20% Y2O3-80% ZrO2 was 1/3 to 1/2 that of 8% Y2O3-92% ZrO2. Both magnesia and calcia stabilized ZrO2 crept at a rate 5 to 10 times that of the 20% Y2O3 material. A near proportionality between creep rate and applied stress was observed. The rate controlling process appeared to be thermally activated, with an activation energy of approximately 100 cal/gm mole K. Creep deformation was due to cracking and particle sliding.

Firestone, R. F.↗

Improved performance thermal barrier coatings

Thermal barrier coatings offer an attractive approach to improving the durability and efficiency of the hot section of heat engines. The coatings typically consist of an inner alloy bond coating about 0.01 cm thick resistant to oxidation and hot corrosion and an outer ceramic layer, usually a stabilized zirconia, 0.01-0.05 cm thick. Here, the materials, thermomechanical stress, and hot corrosion problems associated with thermal barrier coatings are reviewed along with the capabilities and limitations of current technology. The coatings discussed include ZrO2-Y2O3/NiCrAlY, ZrO2-Y2O3/NiCoCrAlY, ZrO2-MgO/NiCoCrAlY, CaO-SiO2/Co-Cr-Al-Y, and CaO-SiO2/NiCrAlY systems. It is emphasized that the performance of thermal barrier coatings is governed by many complex and interrelated factors, so that optimization of these coatings always involves certain tradeoffs.

Levine, S. R.↗

Performance of thermal barrier coatings in high heat flux environments

Thermal barrier coatings were exposed to the high temperature and high heat flux produced by a 30 kW plasma torch. Analysis of the specimen heating rates indicates that the temperature drop across the thickness of the 0.038 cm ceramic layer was about 1100 C after 0.5 sec in the flame. An as-sprayed ZrO2-8%Y2O3 specimens survived 3000 of the 0.5 sec cycles with failing. Surface spalling was observed when 2.5 sec cycles were employed but this was attributed to uneven heating caused by surface roughness. This surface spalling was prevented by smoothing the surface with silicon carbide paper or by laser glazing. A coated specimen with no surface modification but which was heat treated in argon also did not surface spall. Heat treatment in air led to spalling in as early as 2 cycle from heating stresses. Failures at edges were investigated and shown to be a minor source of concern. Ceramic coatings formed from ZrO2-12%Y2O3 or ZrO2-20%Y2O3 were shown to be unsuited for use under the high heat flux conditions of this study.

Miller, R. A.↗

Performance of thermal barrier coatings in high heat flux environments

Thermal barrier coatings were exposed to the high temperature and high heat flux produced by a 30 kW plasma torch. Analysis of the specimen heating rates indicates that the temperature drop across the thickness of the 0.038 cm ceramic layer was about 1100 C after 0.5 sec in the flame. An as-sprayed ZrO2-8 percent Y2O3 specimens survived 3000 of the 0.5 sec cycles with falling. Surface spalling was observed when 2.5 sec cycles were employed but this was attributed to uneven heating caused by surface roughness. This surface spalling was prevented by smoothing the surface with silicon carbide paper or by laser glazing. A coated specimen with no surface modification but which was heat treated in argon also did not surface spall. Heat treatment in air led to spalling in as early as 1 cycle from heating stresses. Failures at edges were investigated and shown to be a minor source of concern. Ceramic coatings formed from ZrO2-12 percent Y2O3 or ZrO2-2O percent Y2O3 were shown to be unsuited for use under the high heat flux conditions of this study.

Miller, R. A.↗

The identification of group II inclusions in carbonaceous chondrites by electron probe microanalysis of perovskite

The technique developed by Kornacki (1984) for identifying group II Ca/Al-rich inclusions in carbonaceous chondrites by electron-microprobe analysis of the ZrO2 or Y2O3 content of their perovskite component is demonstrated using material from 20 Allende inclusions. The results are presented in tables and graphs and compared with findings obtained by other procedures. Group II inclusions are found to have perovskites generally containing less than 0.10 wt pct ZrO2 and/or Y2O3 (average of several grains), while those of groups I, III, V, and VI have more than 0.25 wt pct ZrO2. Analysis of data on eight Allende Ca/Al-rich inclusions shows that 75 percent of the fine-grained inclusions belong to group II. The implications of these findings for fractionation processes in the primitive solar nebula are indicated.

Kornacki, A. S.↗

Performance of thermal barrier coatings in high heat flux environments

Thermal barrier coatings were exposed to the high temperature and high heat flux produced by a 30 kW plasma torch. Analysis of the specimen heating rates indicates that the temperature drop across the thickness of the 0.038 cm ceramic layer was about 1100 C after 0.5 sec in the flame. An as-sprayed ZrO2-8 percent Y203 specimens survived 3000 of the 0.5 sec cycles with failing. Surface spalling was observed when 2.5 sec cycles were employed but this was attributed to uneven heating caused by surface roughness. This surface spalling was prevented by smoothing the surface with silicon carbide paper or by laser glazing. A coated specimen with no surface modification but which was heat treated in argon also did not surface spall. Heat treatment in air led to spalling in as early as 2 cycle from heating stresses. Failures at edges were investigated and shown to be a minor source of concern. Ceramic coatings formed from ZrO2-12 percent Y2O3 or ZrO2-20 percent Y2O3 were shown to be unsuited for use under the high heat flux conditions of this study.

Miller, R. A.↗

Ceramic oxide reactions with V2O5 and SO3

Ceramic oxides are not inert in combustion environments, but can react with, inter alia, SO3, and Na2SO4 to yield low melting mixed sulfate eutectics, and with vanadium compounds to produce vanadates. Assuming ceramic degradation to become severe only when molten phases are generated in the surface salt (as found for metallic hot corrosion), the reactivity of ceramic oxides can be quantified by determining the SO3 partial pressure necessary for molten mixed sulfate formation with Na2SO3. Vanadium pentoxide is an acidic oxide that reacts with Na2O, SO3, and the different ceramic oxides in a series of Lux-Flood type of acid-base displacement reactions. To elucidate the various possible vanadium compound-ceramic oxide interactions, a study was made of the reactions of a matrix involving, on the one axis, ceramix oxides of increasing acidity, and on the other axis, vanadium compounds of increasing acidity. Resistance to vanadium compound reaction increased as the oxide acidity increased. Oxides more acidic than ZrO2 displaced V2O5. Examination of Y2O3- and CeO2-stabilized ZrO2 sintered ceramics which were degraded in 700 C NaVO3 has shown good agreement with the reactions predicted above, except that the CeO2-ZrO2 ceramic appears to be inexplicably degraded by NaVO3.

Jones, R. L.↗