Critical thickness of polymer‐derived ceramic coatings with particulate fillers
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The development of low conductivity, robust thermal and environmental barrier coatings requires advanced testing techniques that can accurately and effectively evaluate coating thermal conductivity and cyclic resistance at very high surface temperatures (up to 17OOOC) under large thermal gradients. In this study, a laser high-heat-flux test approach is established for evaluating advanced low conductivity, ultra-high temperature ceramic thermal and environmental barrier coatings under the NASA Ultra Efficient Engine Technology (UEET) program. The test approach emphasizes the real-time monitoring and assessment of the coating thermal conductivity: the initial conductivity rise under a steady-state high temperature thermal gradient test due to coating sintering, and the later coating conductivity reduction under a subsequent cyclic thermal gradient test due to coating cracking/delamination. The coating system is then evaluated based on the damage accumulations and failure after the combined steady-state and cyclic thermal gradient tests. The lattice and radiation thermal conductivity of advanced ceramic coatings can also be evaluated using laser heat-flux techniques. The coating external radiation resistance is assessed based on the measured specimen temperature response under a laser heated intense radiation flux source. The coating internal radiation contribution is investigated based on the measured apparent coating conductivity increases with the coating surface test temperature under large thermal gradient test conditions. Since an increased radiation contribution is observed at these very high surface test temperatures, by varying the laser heat-flux and coating average test temperature, the complex relation between the lattice and radiation conductivity as a function of surface and interface test temperature is derived.
High temperature fiber-reinforced ceramic matrix composites (CMCs) are important for aerospace applications because of their low density, high strength, and significantly higher-temperature capabilities compared to conventional metallic systems. The use of the SiCf/SiC and Cf/SiC CMCs allows the design of lighter-weight, more fuel efficient aircraft engines and also more advanced spacecraft airframe thermal protection systems. However, CMCs have to be protected with advanced environmental barrier coatings when they are incorporated into components for the harsh environments such as in aircraft engine or spacecraft applications. In this study, high temperature oxidation kinetics of an advanced HfSiCN coating on Cf/SiC CMC substrates were investigated at 1300 C, 1400 C, and 1500 C by using thermogravimetric analysis (TGA). The coating oxidation reaction parabolic rate constant and activation energy were estimated from the experimental results. The oxidation reaction studies showed that the coatings formed the most stable, predominant HfSiO4-HfO2 scales at 1400 C. A peroxidation test at 1400 C then followed by subsequent oxidation tests at various temperatures also showed more adherent scales and slower scale growth because of reduced the initial transient oxidation stage and increased HfSiO4-HfO2 content in the scales formed on the HfSiCN coatings.
Lubrication with inorganic binders used for coatings exposed to high temperatures
The results of an experimental and analytical evaluation of ceramic turbine tip shrouds within a small turbine engine operating environment are presented. The ceramic shrouds were subjected to 1001 cycles between idle and high power and steady-state conditions for a total of 57.8 engine hr. Posttest engine inspection revealed mud-flat surface cracking, which was attributed to microcracking under tension with crack penetration to the ceramic and bond coat interface. Sections and micrographs tend to corroborate the thesis. The engine test data provided input to a thermomechanical analysis to predict temperature and stress profiles throughout the ceramic gas-path seal. The analysis predicts cyclic thermal stresses large enough to cause the seal to fail. These stresses are, however, mitigated by inelastic behavior of the shroud materials and by the microfracturing that tensile stresses produce. Microfracturing enhances shroud longevity during early life but provides the failure mechanism during life but provides the failure mechanism during extended life when coupled with the time dependent inelastic materials effects.
An analysis was made to determine the potential benefits of using a ceramic thermal insulation coating of calcia-stabilized zirconia on cooled engine parts. The analysis was applied to turbine vanes of a high temperature and high pressure core engine and a moderate temperature and low pressure research engine. Measurements made during engine operation showed that the coating substantially reduced vane metal wall temperatures. Evaluation of the durability of the coating on turbine vanes and blades in a furnace and engine were encouraging.
A copper base insert coated with a layer of aluminum oxide ceramic prevents frictional binding between the gate and base surfaces of a gate valve which are subject to rapid sliding action and high temperatures.
The first batches of ion traps patterned and coated were processed per the standard 3-step clean, air fire, and metallization processes. The third or fourth lot using this process resulted in poorly adhering metallization. Up until this point, the standard process was used to metallize and pattern ceramic ion traps without fail. At about the 4th batch of parts something changed. After the 5th batch, the ceramic ion traps received generally came with some unknown contamination that does not come off in a standard 3-step clean (Lenium Vapor Degreaser, Acetone, IPA) and air fire (860C for 1 hour) for which this process removes the vast majority of all contamination for most ceramic metallization. This is highly unusual. Using HF + Boiling H 2 O 2 is extreme for cleaning the ceramic ion traps. The contamination was never identified and is stubborn to effectively clean. Standard as-fired ceramic should be very easy to clean as if s fired at temperatures greater than 1400°C and not much in terms of contamination should exist at these temperatures, so there must be an intermediate step/process which is imparting this contamination. It is likely a polishing compound or previous polishing contaminant, but also not easily visually distinguishable until after metallization. The halo marks observed on parts might be fingerprints (less likely) or potential polishing marks (more likely) as metallization typically doesn't cover/hide any damage or contamination, but rather quite clearly the opposite, it accentuates it. Blotchy appearances in the metallization usually indicated an adhesion issue. As a result of the fragility of the parts (yield loss due to handling) and difficulty in identifying the contamination during cleaning, we have taken a conservative approach of HF + H 2 O 2 cleaning for all batches after the contamination and adhesion issues were identified.
Six types of uncoated ceramic fibers were static tensile and tensile creep tested at various elevated temperatures. Three types of boron nitride coated fibers were also tested. Room temperature static tensile tests were initially performed on all fibers, at gage lengths of 1, 2, and 4 inches, to determine the magnitude of end effects from the gripping system used. Tests at one elevated temperature, at gage lengths of 8 and 10 inches, were also conducted, to determine end effects at elevated temperatures. Fiber cross sectional shapes and areas were determined using scanning electron microscopy. Creep testing was typically performed for 4 hours, in an air atmosphere.
An emerging new class of promising materials, High-Entropy Ceramics (HECs) or Compositionally-Complex Ceramics (CCCs), have been successfully fabricated in the last three years. This project evaluates HECs/CCCs in the concentrated solar power (CSP) context. In this project, we have identified a couple of simple, and key descriptors governing thermal conductivity in HECs. Size disorder among the cations was found to have a strong influence on the thermal conductivity across multiple systems and throughout a vast compositional space. Since identifying this, we have optimized previous compositions to achieve low thermal conductivities of $k$~$1-1.4Wm{-1}K{-1}$. We have further reduced our selection of promising compositions based on project guidelines and applied a theory that can potentially predict reactivity with molten salts to identify a small set of HECs that are suitable for further molten salt heat transfer media (HTM) stability testing. Many compositions reveal poor resistance to molten chloride salt after being exposed for 24 h compared to the reference structural alloy, Haynes 230. However, after 100 h, a few HECs/CCCs show strong parabolic rate constant effects and provide greater resistance to chloride salt compared to Haynes 230 alloy, which shows more linear kinetics. Postmortem characterization of the microstructure reveals the parabolic rate constant originates from a dense reaction layer form at the interface. This feature is absent in Haynes 230, which only shows grain boundary infiltration. The HECs/CCCs were also put in contact with the metal alloy under Ar for 800 h at 800°C and show negligible interaction. Lastly, parabolic rate constant HECs/CCCs also have low thermal conductivity $(<2 Wm^{-1} K^{-1})$ at 800°C. These specimens satisfy all project requirements and demonstrate their promising application in next-generation CSP.
Dispersed copper phase increases the thermal shock resistance of a plasma-arc-sprayed coating of zirconia used as a heat barrier on a metal substrate. A small amount of copper is deposited on the granules of the zirconia powder before arc-spraying the resultant powder composite onto the substrate.
Coatings, consisting of zirconia powder bonded with orthophosphoric acid and a small amount of hydrofluoric acid, are hard, strong, and refractory, resist thermal shock, and provide good thermal protection. After the aqueous coating is applied to a metallic surface, only a 600 deg F cure is required before service.
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Cylindrical rocket thrust chamber cylinders were coated with a 0.203 mm (0.008 in.) layer of zirconium oxide using a process that employed electrodeposition of metal to a spray coated mandrel. The cylinders were cyclically tested using hydrogen oxygen propellants at a nominal chamber pressure of 4.14 MN/sq m (600 psia) to show the effect of the coating on life. Both cylinders failed prematurely due to causes unrelated to the coatings. Post destructive analysis showed no cooling passage wall deformation. Where erosion of the coating occurred, the coating thickness stabilized at 0.061 mm (0.0024 in.) within 80 cycles and remained well adhered throughout the tests.
Two cylindrical rocket thrust chamber cylinders were coated with a 0.203 mm layer of zirconium oxide using a process that employed electrodeposition of metal to a spray-coated mandrel. The cylinders were cyclically tested using hydrogen-oxygen propellants at a nominal chamber pressure of 4.14 MN/sq m to show the effect of the coating on life. Both cylinders failed prematurely due to causes unrelated to the coatings. Post destructive analysis showed no cooling passage wall deformation. Where erosion of the coating occurred, the coating thickness stabilized at 0.061 mm within 80 cycles and remained well adhered throughout the tests. The hot-gas-side metal wall temperature and the theoretical maximum effective strain were reduced by 80 and 92%, respectively, where the coating was 0.203 mm thick and by 40 and 50%, respectively, where the coating was 0.061 mm thick compared to an uncoated cylinder. The 50 and 92% reductions in maximum effective strain resulted in theoretical lives of 1900 cycles and greater than 10,000 cycles, respectively, compared to 300 cycles for the uncoated cylinder.
Surface catalytic efficiencies of glassy coatings were determined from a reaction boundary layer computation and arc-jet data. The catalytic efficiencies of the various coatings examined are discussed in terms of their reaction-rate constants. These constants are a function of the wall temperature (1290 K to 2000 K). In addition, the advantage of a thermal protection system for a bent biconic, aeroassisted orbital transfer vehicle with a low surface catalytic efficiency is discussed.
This paper presents an analysis of the interface stress in plasma-sprayed zirconia coatings. The stress distributions along smooth and rough interfaces were calculated for perfectly bonded materials. The effect of mechanial interlock along the interface was also calculated. The interface stresses for noninterlocking interfaces were consistently higher; the interlocking interfaces showed high stresses in small regions only.