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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 73 records · Page 4

The preparation of new perfluoro ether fluids exhibiting excellent thermal-oxidative stabilities

A series of low molecular weight perfluoroalkyl ethers (PFAEs) were synthesized by direct fluorination. Viscosity-temperature properties and oxidation stabilities were determined. Viscosity-temperature correlations indicated that increases in branching and increases in the size of the branching substituent caused a deterioration in viscometric properties (i.e., an increase in ASTM slope). In addition, increasing the ratio of carbon to oxygen in these compounds also increased the ASTM slope. Preliminary oxidation stability measurements indicated that highly branched PFAE fluids (i.e., those containing quaternary carbons) may be less stable than either those containing a single trifluoromethyl pendant group or those containing no branching at all.

Jones, William R., Jr.↗

Effect of Metal Alloys, Degradation Inhibitors, Temperatures on Thermal Oxidative Stability of CF3O(CF2O)(sub x)(CF2O)(sub y)CF3 Fluids

Degradation-promoting action of a series of ferrous and titanium alloys on CF3O(CF2O)(sub x)(CF2-CF2O)(sub y)CF3-based Z25 fluids and the inhibition effectiveness of several classes of additives were investigated. Four types of additives-phosphines, phosphates, phospha-s-triazines, and diphosphatetraazacyclooctatetraene-were studied in two batches of Z25 fluid, P28 and P151. In the absence of inhibitors, titanium alloys were more detrimental than the ferrous metals, but the additives were more effective in the presence of titanium alloys. Phosphate esters totally inhibited the decomposition of P151 at 330 C over 24 h in both types of alloys. The other additives were effective at lower temperatures. The responsiveness of fluid to an additive was found to be batch dependent.

Jones, William R., Jr.↗

Graphite Sheet Coating for Improved Thermal Oxidative Stability of Carbon Fiber Reinforced/PMR-15 Composites

Expanded graphite was compressed into graphite sheets and used as a coating for carbon fiber reinforced PMR-15 composites. BET analysis of the graphite indicated an increase in graphite pore size on compression, however the material was proven to be an effective barrier to oxygen when prepegged with PMR-15 resin. Oxygen permeability of the PMR-15/graphite was an order of magnitude lower than the compressed graphite sheet. By providing a barrier to oxygen permeation, the rate of oxidative degradation of PMR-15 was decreased. As a result, the composite thermo-oxidative stability increased by up to 25%. The addition of a graphite sheet as a top ply on the composites yielded little change in the material's flexural strength or interlaminar shear strength.

Campbell, Sandi↗

Moisture-Induced Delamination Video of an Oxidized Thermal Barrier Coating

PVD TBC coatings were thermally cycled to near-failure at 1150 C. Normal failure occurred after 200 to 300 1-hr cycles with only moderate weight gains (0.5 mg/sq cm). Delamination and buckling was often delayed until well after cooldown (desktop spallation), but could be instantly induced by the application of water drops, as shown in a video clip which can be viewed by clicking on figure 2 of this report. Moisture therefore plays a primary role in delayed desktop TBC failure. Hydrogen embrittlement is proposed as the underlying mechanism.

Smialek, James L.↗

Moisture-Induced Delamination Video of an Oxidized Thermal Barrier Coating

PVD TBC coatings were thermally cycled to near-failure at 1150 C. Normal failure occurred after 200-300 1-hr cycles with only moderate weight gains (0.5 mg/cm2). Delamination and buckling was often delayed until well after cooldown (desktop spallation), but could be instantly induced by the application of water drops, as shown in an accompanying video-recording. Moisture therefore plays a primary role in delayed desktop TBC failure. Hydrogen embrittlement is proposed as the underlying mechanism.

Smialek, James L.↗

Thermal expansion of nickel oxide.

Thermal expansion of polycrystalline nickel oxide in oxygen atmosphere with 5 percent nitrogen to 1930 degrees C, noting grain size

HIGH TEMPERATURE AIR↗

Thermal expansion mismatch and oxidation in thermal barrier coatings

Thermal barrier coatings (TBC) for advanced gas turbine blades have been under intensive development during the last several years. This investigation is intended to achieve a clearer understanding of the mechanical behavior of plasma sprayed zirconia-yttria TBCs, involving a nickle-chromium-aluminum bond coat. The near term objectives are to study the stress states in a relatively simple model TBC subjected to steady state thermal loading. The resulting thermal expansion mismatch and oxidation have been primary targets for the study. The finite element approach and the effects of thermal mismatch and oxidation are described. A proposed mechanism for oxidation induced coating failure is also presented.

Chang, G. C.↗

Microwave Regeneration and Thermal and Oxidative Stability of Imidazolium Cyanopyrrolide Ionic Liquid for Direct Air Capture of Carbon Dioxide

Abstract Understanding the oxidative and thermal degradation of CO 2 sorbents is essential for assessing long‐term sorbent stability in direct air capture (DAC). The potential degradation pathway of imidazolium cyanopyrrolide, an ionic liquid (IL) functionalized for superior CO 2 capacity and selectivity, is evaluated under accelerated degradation conditions to elucidate the secondary reactions that can occur during repetitive absorption‐desorption thermal‐swing cycles. The combined analysis from various spectroscopic, chromatographic, and thermal gravimetric measurements indicated that radical and S N 2 mechanisms in degradation are encouraged by the nucleophilicity of the anion. Thickening of the liquid and gas evolution are accompanied by 50 % reduction in CO 2 capacity after a 7‐day exposure to O 2 under 80 °C. To prevent long exposure to conventional thermal heating, microwave (MW) regeneration of the CO 2 ‐reactive IL is used, where dielectric heating at 80 and 100 °C rapidly desorbs CO 2 and regenerates the IL without any measurable degradation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Stress generation in thermally grown oxide films

A three dimensional finite element analysis was conducted, using the ANSYS computer program, of the stress state in a thin oxide film thermally formed on a rectangular piece of NiCrAl alloy. The analytical results indicate a very high compressive stress in the lateral directions of the film (approximately 6200 MPa), and tensile stresses in the metal substrate that ranged from essentially zero to about 55 MPa. It was found further that the intensity of the analytically determined average stresses could be approximated reasonably well by the modification of an equation developed previously by Oxx for stresses induced into bodies by thermal gradients.

Kumnick, A. J.↗

Rare-earth doped thermal barrier coating bond coat for thermally grown oxide luminescence sensing

A thermal barrier coated component, such as a turbine blade formed from a superalloy substrate, includes a thermal barrier coating applied onto the substrate. A metallic bond coat layer is on the substrate and includes rare-earth luminescent dopants. A ceramic top coat layer is on the bond coat layer. A temperature sensing thermally grown oxide (TGO) layer is formed at the interface of the bond coat layer and ceramic top coat layer. The temperature sensing TGO layer includes grown rare-earth luminescent ions migrated from the metallic bond coat layer in an amount sufficient to enable luminescence sensing of the TGO layer for real-time phosphor thermometry temperature measurements at the TGO layer.

Fouliard, Quentin↗

Thermally Grown Oxide Stress in PS-PVD and EB-PVD Thermal Barrier Coatings Observed at Various Lifetimes Via Synchrotron X-ray Diffraction

The current standard application method for thermal barrier coatings (TBCs) on turbine blades for jet engines is electron-beam physical vapor deposition (EB-PVD) due to its high strain tolerance and low thermal conductivity. An emerging deposition method, plasma-spray physical vapor deposition (PS-PVD), presents an opportunity for a tailorable microstructure, and non-line-of-sight deposition that is faster and less expensive. To compare the lifetime behavior of both PS-PVD and EB-PVD coatings, samples subjected to 300 and 600 thermal cycles were measured during a 1 h thermal cycle to determine the strains, which were converted to stress, in the thermally grown oxide (TGO) layer of the TBCs using synchrotron X-ray diffraction (XRD). Room temperature XRD measurements indicated among samples that PS-PVD coatings experienced greater variation in in-plane room temperature strain in the TGO after cycling than the EB-PVD coatings. In-situ XRD measurements indicated similar high-temperature strain and no spallation after 600 thermal cycles for both coatings. Further, microscopy imaging after cycling showed greater rumpling in PS-PVD coatings that led to different failure modes between the two coatings’ TGO layers. The tailorability of PS-PVD coatings allows for adjustments in the processing parameters to improve their overall performance after aging and bridge the differences between the two deposition methods.

36 MATERIALS SCIENCE↗

Furnace Cyclic Behavior of Plasma-Sprayed Zirconia-Yttria and Multi-Component Rare Earth Oxide Doped Thermal Barrier Coatings

Ceramic thermal barrier coatings will play an increasingly important role in advanced gas turbine engines because of their ability to enable further increases in engine temperatures. However, the coating performance and durability become a major concern under the increasingly harsh thermal cycling conditions. Advanced zirconia- and hafnia-based cluster oxide thermal barrier coatings with lower thermal conductivity and improved thermal stability are being developed using a high-heat-flux laser-rig based test approach. Although the new composition coatings were not yet optimized for cyclic durability, an initial durability screening of numerous candidate coating materials was carried out using conventional furnace cyclic tests. In this paper, furnace thermal cyclic behavior of the advanced plasma-sprayed zirconia-yttria-based thermal barrier coatings that were co-doped with multi-component rare earth oxides was investigated at 1163 C using 45 min hot cycles. The ceramic coating failure mechanisms were studied by using scanning electron microscopy combined with X-ray diffraction phase analysis after the furnace tests. The coating cyclic lifetime will be discussed in relation to coating phase structures, total dopant concentrations, and other properties.

Zhu, Dongming↗

Platinum on High-Entropy Aluminate Spinels as Thermally Stable CO Oxidation Catalysts

Thermal degradation is a leading cause of automotive catalyst deactivation. Because high-entropy oxides are uniquely stabilized at high temperatures via an increase in configurational entropy, these materials may offer new mechanisms for preventing the thermal deactivation of precious metal catalysts. In this work, we evaluated platinum loaded on simple and high-entropy aluminate spinels (MAl 2 O 4 , where M = Co, Cu, Mg, Ni, or mixtures thereof) in carbon monoxide oxidation before and after aging at 800 °C. Pt supported on all simple spinels showed significant deactivation after thermal aging compared to the fresh samples, with T 90 increasing by at least 60 °C. However, Pt on high-entropy spinels had nearly the same or better activity after aging, with T 90 increasing by only 6 °C at most. During aging and reduction, copper exsolved from the spinel supports and alloyed with platinum. This interaction promoted low temperature oxidation activity, presumably through weakened CO binding, but did not prevent deactivation. On the other hand, Co, Mg, and Ni constituents promoted stronger CO bonding, as evidenced by apparent negative order kinetics and poor activity at low temperatures. High-entropy spinels, containing a variety of active metals, displayed synergetic reactant adsorption capacity and cooperative effects with supported platinum particles, which collectively prevented thermal deactivation.

CO oxidation↗

Effects of Doping on Thermal Conductivity of Pyrochlore Oxides for Advanced Thermal Barrier Coatings

Pyrochlore oxides of general composition, A2B2O7, where A is a 3(+) cation (La to Lu) and B is a 4(+) cation (Zr, Hf, Ti, etc.) have high melting point, relatively high coefficient of thermal expansion, and low thermal conductivity which make them suitable for applications as high-temperature thermal barrier coatings. The effect of doping at the A site on the thermal conductivity of a pyrochlore oxide La2Zr2O7, has been investigated. Oxide powders of various compositions La2Zr2O7, La(1.7)Gd(0.3)Zr2O7, La(1.7)Yb(0.3)Zr2O7 and La(1.7)Gd(0.15)Yb(0.15)Zr2O7 were synthesized by the citric acid sol-gel method. These powders were hot pressed into discs and used for thermal conductivity measurements using a steady-state laser heat flux test technique. The rare earth oxide doped pyrochlores La(1.7)Gd(0.3)Zr2O7, La(1.7)Yb(0.3)Zr2O7 and La(1.7)Gd(0.15)Yb(0.15)Zr2O7 had lower thermal conductivity than the un-doped La2Zr2O7. The Gd2O3 and Yb2O3 co-doped composition showed the lowest thermal conductivity.

Bansal, Narottam P.↗