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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 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Phase-field modeling of thermally-grown oxide and damage evolution in environmental barrier coatings

Silicon carbide-based ceramic matrix composites protected by environmental barrier coatings (EBCs) present a promising materials solution for next-generation gas turbines. Developing more robust and efficient EBCs is therefore of significant technological importance. During the service in high-temperature oxidative environments, there is a thermally grown oxide (TGO) layer, spontaneously formed in the EBC system. TGO is recognized as a critical factor for the degradation and failure of EBCs, yet the detailed mechanisms of TGO growth and its effect on EBC failure remain unclear. In this study we develop a comprehensive chemo-mechano-phase-field model to simulate growth of the TGO in EBCs, factoring in creep and deformation, and especially the cracking behaviors. The volume expansion due to TGO growth and the resulting large inelastic deformation are addressed by using our recently developed, so-called incremental realization of inelastic deformation (IRID) algorithm, in combination with an adapted Hu-Chen spectral solver for elasticity. Simulations of TGO growth are performed considering different growth modes of TGOs determined mainly by the ratio of oxidant permeability in the topcoat to that in the TGO itself. Large-scale three-dimensional (3D) simulations are performed to model the formation of interconnecting vertical/channel cracks (often called ‘mud cracks’). The simulated crack morphology are in excellent agreement with the experimental observations from the literature. The simulations also provide insights into the cracking of EBCs and its dependence on the structure and constituent properties of the coating system. Furthermore, these results demonstrate the developed damage model can be a useful tool for design of more durable EBCs.

Cracking↗
NASA NTRS1984

Thermal and Oxidative Stabilities of Liquid Lubricants

The fundamental processes which occur during the thermal and oxidation degradation of hydrocarbons is reviewed. Various classes of liquid lubricants such as mineral oils, esters, polyphenyl ethers, C-ethers, and fluorinated polyethers are emphasized. Techniques to determine thermal and oxidative stabilities of lubricants are discussed. The role of inhibitors and catalysis is examined.

Jones, W. R., Jr.↗
NASA NTRS1982

Thermal and oxidative degradation studies of formulated C-ethers by gel-permeation chromatography

Gel-permeation chromatography was used to analyze C-ether lubricant formulations from high-temperature bearing tests and from micro-oxidation tests. Three mu-styragel columns (one 500 and two 100 A) and a tetrahydrofuran mobile phase were found to adequately separate the C-ether degradation products. The micro-oxidation tests yielded degradation results qualitatively similar to those observed from the bearing tests. Micro-oxidation tests conducted in air yielded more degradation than did tests in nitrogen. No great differences were observed between the thermal-oxidative stabilities of the two C-ether formulations or between the catalytic degradation activities of silver and M-50 steel. C-ether formulation I did yield more degradation than did formulation II in 111- and 25-hour bearing tests, respectively.

Jones, W. R., Jr.↗
NASA NTRS1992

Ultrasonic and micromechanical study of damage and elastic properties of SiC/RBSN ceramic composites

Ultrasonic techniques are employed to develop methods for nondestructive evaluation of elastic properties and damage in SiC/RBSN composites. To incorporate imperfect boundary conditions between fibers and matrix into a micromechanical model, a model of fibers having effective anisotropic properties is introduced. By inverting Hashin's (1979) microstructural model for a composite material with microscopic constituents the effective fiber properties were found from ultrasonic measurements. Ultrasonic measurements indicate that damage due to thermal shock is located near the surface, so the surface wave is most appropriate for estimation of the ultimate strength reduction and critical temperature of thermal shock. It is concluded that bonding between laminates of SiC/RBSN composites is severely weakened by thermal oxidation. Generally, nondestructive evaluation of thermal oxidation effects and thermal shock shows good correlation with measurements previously performed by destructive methods.

Chu, Y. C.↗
NASA NTRS2012

Aqueously Dispersed Silver Nanoparticle-Decorated Boron Nitride Nanosheets for Reusable, Thermal Oxidation-Resistant Surface Enhanced Raman Spectroscopy (SERS) Devices

The impurity-free aqueous dispersions of boron nitride nanosheets (BNNS) allowed the facile preparation of silver (Ag) nanoparticle-decorated BNNS by chemical reduction of an Ag salt with hydrazine in the presence of BNNS. The resultant Ag-BNNS nanohybrids remained dispersed in water, allowing convenient subsequent solution processing. By using substrate transfer techniques, Ag-BNNS nanohybrid thin film coatings on quartz substrates were prepared and evaluated as reusable surface enhanced Raman spectroscopy (SERS) sensors that were robust against repeated solvent washing. In addition, because of the unique thermal oxidation-resistant properties of the BNNS, the sensor devices may be readily recycled by short-duration high temperature air oxidation to remove residual analyte molecules in repeated runs. The limiting factor associated with the thermal oxidation recycling process was the Ostwald ripening effect of Ag nanostructures.

Lin, Yi↗
DOE OSTI2020

Microscopic Observation of Solid Electrolyte Interphase Bilayer Inversion on Silicon Oxide

Silicon has been investigated in recent years as an alloying anode material to enhance gravimetric energy density in lithium-ion batteries. Although recent developments have suggested that silicon oxides exhibit improved cycling stability over pure Si, the origin of the improved cycling performance is still poorly understood. The initial solid electrolyte interphase (SEI) formation mechanisms on Si wafers with both native oxide and chemically etched thermal oxide coatings are investigated structurally, chemically, and morphologically in the nanoscale. After one electrochemical cycle, microscopy reveals that SEI formed on native SiO x features the typical SEI bilayer structure with a carbon-rich outer SEI layer and an inorganic-rich inner SEI layer. In contrast, the SEI formed on chemically etched thermal oxide shows an inversion in the structure. This work observes distinct initial SEI formation mechanisms on the HF-etched SiO 2 surface, which may be partially responsible for improved cycle life observed in SiO x -based anode materials.

25 ENERGY STORAGE↗
DOE OSTI2021

Spectroscopic insight into carbon speciation and removal on a Cu/BEA catalyst during renewable high-octane hydrocarbon synthesis

Conversion of methanol and dimethyl ether (DME) to high-octane gasoline catalyzed by beta zeolite (BEA) provides an opportunity for the production of high-quality fuels from renewable carbon sources (e.g., gasified biomass). Recent research demonstrated that a Cu-modified BEA zeolite catalyst (Cu/BEA) offered advantages over the unmodified BEA catalyst due to multifunctional Cu species that enabled incorporation of co-fed H2, reactivation of light alkanes, and reduction of products from the aromatic hydrocarbon pool. The shift in hydrocarbon pool chemistry has the potential to influence the identity and relative composition of surface carbon species that are often linked to deactivation. A detailed understanding of these carbon species is important to develop an effective and efficient regeneration procedure that can enable the transition from fundamental catalyst development to commercial application. Here, we applied complementary ex situ and in situ characterization techniques to compare the structures of surface carbon species on post-reaction Cu/BEA and unmodified BEA catalysts. Both catalysts contained acyclic and aromatic hydrocarbons along with graphitic carbon species. However, the post-reaction Cu/BEA catalyst had a lower polycyclic aromatic content, and further, the graphitic species were more hydrogenated and defective. It was also found that the presence of Cu promoted carbon removal at lower temperatures than for unmodified BEA through activation of O2 by Cu oxide during thermal oxidation. The fundamental insight into the composition of surface carbon species enabled the design of an effective and efficient regeneration strategy for the DME homologation reaction over Cu/BEA, resulting in full recovery of the catalyst activity.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗
NASA NTRS1987

The localization and crystallographic dependence of Si suboxide species at the SiO2/Si interface

X-ray photoemission spectroscopy has been used to examine the localization and crystallographic dependence of Si(+), Si(2+), and Si(3+) suboxide states at the SiO2/Si interface for (100)and (111)-oriented substrates with gate oxide quality thermal oxides. The Si(+) and Si(2+) states are localized within 6-10 A of the interface while the Si(3+) state extends about 30 A into the bulk SiO2. The distribution of Si(+) and Si(2+) states shows a strong crystallographic dependence with Si(2+) dominating on (100) substrates and Si(+) dominating on (111) substrates. This crystallographic dependence is anticipated from consideration of ideal unreconstructed (100) and (111) Si surfaces, suggesting that (1) the Si(+) and Si(2+) states are localized immediately within the first monolayer at the interface and (2) the first few monolayers of substrate Si atoms are not significantly displaced from the bulk. The total number of suboxide states observed at the SiO2/Si interface corresponds to 94 and 83 percent of a monolayer for these (100) and (111) substrates, respectively.

Grunthaner, P. J.↗
NASA NTRS1997

Ceramic Matrix Composites: High Temperature Effects. (Latest Citations from the Aerospace Database)

The bibliography contains citations concerning the development and testing of ceramic matrix composites for high temperature use. Tests examining effects of the high temperatures on bond strength, thermal degradation, oxidation, thermal stress, thermal fatigue, and thermal expansion properties are referenced. Applications of the composites include space structures, gas turbine and engine components, control surfaces for spacecraft and transatmospheric vehicles, heat shields, and heat exchangers.

HIGH TEMPERATURE TESTS↗
NASA NTRS1972

Oxidation and thermal fatigue of coated and uncoated NX-188 nickel-base alloy in a high velocity gas stream

A cast nickel-base superalloy, NX-188, coated and uncoated, was tested in a high-velocity gas stream for resistance to oxidation and thermal fatigue by cycling between room temperature and 980, 1040, and 1090 C. Contrary to the behavior of more conventional nickel-base alloys, uncoated NX-188 exhibited the greatest weight loss at the lowest test temperature. In general, on the basis of weight change and metallographic observations a coating consisting of vapor-deposited Fe-Cr-Al-Y over a chromized substrate exhibited the best overall performance in resistance to oxidation and thermal fatigue.

Johnson, J. R.↗
NASA NTRS2018

Coupled Thermomechanical Micromechanics Modeling of the Influence of Thermally Grown Oxide Layer in an Environmental Barrier Coating System

Environmental Barrier Coatings (EBCs) have emerged as a promising means of protecting critical components for high temperature applications (e.g., aircraft engines). EBCs are often used to protect an underlying material (substrate) from extreme thermal/chemical environments. However, systems that utilize EBCs are susceptible to a number of failure modes including oxidation/delamination. Environmental Barrier Coatings (EBCs) have emerged as a promising means of protecting silicon based ceramic matrix composite (CMC) components for high temperature applications (e.g., aircraft engines). EBCs are often used to protect an underlying material (substrate) such as silicon carbide from extreme thermal/chemical environments. In a typical CMC/EBC system, an EBC may or may not be adhered to an underlying substrate with a bond coat (e.g., silicon). Irrespective, systems that utilize EBCs are susceptible to a number of failure modes including oxidation/delamination, recession, chemical attack and dissolution, thermo-mechanical degradation, erosion, and foreign object damage. Current work at NASA Glenn Research Center is aimed at addressing these failure modes in EBC systems and developing robust analysis tools to aid in the design process. The Higher-Order Theory for Functionally Graded Materials (HOTFGM), a precursor to the High-Fidelity Generalized Method of Cells micromechanics approach, was developed to investigate the coupled thermo-mechanical behavior of functionally graded composites and will be used herein to assess the development and growth of a low-stiffness thermally grown oxide (TGO) layer in EBC/CMC systems without a silicon bond coat. To accomplish this a sensitivity study is conducted to examine the influence of uniformly and non-uniformly grown oxide layer on the associated driving forces leading to mechanical failure (spallation) of EBC layer when subjected to isothermal loading, recession, chemical attack and dissolution, thermomechanical degradation, erosion, and foreign object damage. Current work at NASA Glenn Research Center is aimed at addressing these failure modes in EBC systems and developing robust analysis tools to aid in the design process. The Higher-Order Theory for Functionally Graded Materials (HOTFGM), a precursor to the High-Fidelity Generalized Method of Cells micromechanics approach, was developed to investigate the coupled thermo-mechanical behavior of functionally graded composites (Aboudi et al., 1999, Composites B). For example, HOTFGM was previously used (Arnold et al, 1995, NASA CP 10178, paper 34), to assess interlaminar stresses (including free edge effects) in a substrate with a thermal barrier coating (TBC). In this study, HOTFGM micromechanics analyses will be used to assess the development and growth of a low-stiffness thermally grown oxide (TGO) layer between a silicon carbide substrate and a ytterbium disilicate EBC. In order to realistically simulate TGO growth, an evolution law will be incorporated into HOTFGM. In addition, the effect of TGO roughness will be explored consistent with previous TBC work (Pindera et al., 2000. Material Science and Engineering, A284, pp. 158-175). This model represents a first step in developing a robust analysis tool that can ultimately be used to design durable EBC systems. Additional failure modes will be considered as part of a future work.

environmental barrier coating↗
DOE OSTI2023

Grain size dependence of thermally induced oxidation in zirconium carbide

Here complementary analytical approaches were employed to probe the effect of grain size on thermally induced oxidation of zirconium carbide (ZrC) utilizing thermogravimetric analysis, differential scanning calorimetry, and Raman spectroscopy, as well as synchrotron-based and laboratory-based X-ray diffraction (XRD) experiments. The oxidation mechanism and phase behavior of nanocrystalline ZrC (grain size ~ 20 nm) were compared with that of the more documented microcrystalline ZrC (grain size ~ 1 µm). Synchrotron XRD at the Advanced Photon Source with a hydrothermal diamond anvil cell (HDAC) used as a sample chamber revealed that the onset of oxidation is at ~ 380 °C for microcrystalline ZrC which is in agreement with previous work. In contrast, the critical oxidation temperature was ~ 330 °C for nanocrystalline ZrC. Additional high-temperature synchrotron XRD experiments at the National Synchrotron Light Source II using a lamp furnace in combination with Raman analysis showed that tetragonal ZrO 2 forms as an initial oxidation product and transforms at higher temperatures to the monoclinic phase. Thermogravimetric analysis (TGA) coupled with differential scanning calorimetry (DSC) confirmed the X-ray results of a lower critical oxidation temperature for the nanocrystalline sample. The phase transformations in the oxide phase with associated critical temperatures were also evident in the thermodynamic data as exothermic heat events.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
NASA NTRS1982

Effect of some nitrogen compounds thermal stability of jet A

The effect of known concentrations of some nitrogen containing compounds on the thermal stability of a conventional fuel, namely, Jet A was investigated. The concentration range from 0.01 to 0.1 wt% nitrogen was examined. Solutions were made containing, individually, pyrrole, indole, quinoline, pyridine, and 4 ethylpyridine at 0.01, 0.03, 0.06, and 0.1 wt% nitrogen concentrations in Jet A. The measurements were all made by using a standard ASTM test for evaluating fuel thermal oxidation behavior, namely, ASTM D3241, 'thermal oxidation stability of turbine fuels (JFTOT procedure).' Measurements were made at two temperature settings, and 'breakpoint temperatures' were determined. The results show that the pyrrole and indole solutions have breakpoint temperatures substantially lower than those of the Jet A used.

Antoine, A. C.↗
DOE OSTI2025

Unusual Electrochemical Activity of Thin SiO 2 Layers Leads to Instability of Molecular Attachment in Hybrid Photoelectrodes

Hybrid photoelectrodes, comprised of a light-absorbing semiconductor and a surface-integrated molecular catalyst, are attractive for applications in artificial photosynthesis, since they combine the advantages of broadband semiconductor light absorption with the selectivity of molecular catalysis. A widely used class of hybrid photoelectrodes is based on Si substrates passivated by a thin (<3 nm) layer of silicon oxide, which is commonly prepared by controlled chemical or thermal oxidation, resulting in chemical oxide (ChO) or thermal oxide (ThO) layers, respectively. However, the electrochemical stability of these oxide layers, and the chemical stability of the semiconductor-molecule assembly in hybrid photoelectrodes, are not well understood, with evidence that covalently-bound molecules detach from the oxide surface upon application of cathodic bias. We have examined the intrinsic electrochemical reactivity of silicon oxide layers and how it affects the attachment of molecular monolayers. We determined that the surface of Si|ThO is primarily terminated with hydrophobic siloxane moieties, whereas that of Si|ChO contains a higher concentration of hydrophilic silanol groups. Initial high current densities for Si|ChO under applied bias up to -2 V vs. Ag/AgCl, decrease during repeated cyclic voltammetry scans, due to the consumption of surface-bound water. This is manifested by a reversible wave around -0.5 V in CH 3 CN solution, and a similar pH-dependent wave in water, revealing the pK a of the silanol groups to be ~4. Here, our combined observations support the electrochemically-induced dehydration of the SiO 2 surface, which converts silanol groups to siloxanes and proceeds through an H-atom intermediate that is most likely stabilized by pentavalent Si. We propose that similar reactivity is responsible for the electrochemical loss of alkylsiloxane-attached molecules under cathodic bias, which has important implications for the choice of catalyst attachment strategy in hybrid photoelectrodes.

14 SOLAR ENERGY↗
DOE OSTI2023

Oxide derived Cu nanofibril assembly for enhanced nonenzymatic glucose sensing

In this report, we have prepared copper nanofibril assembly via thermal oxidation followed by electrochemical reduction processes, exhibiting superior glucose detection ability. The morphological analysis evidenced the formation of rough islands or nanofibril structure on the Cu surface depending on initial thermal oxidation temperature. The glucose detection performance was investigated by performing cyclic voltammetry and chronoamperometry with varying glucose concentration. A high sensitivity (4131.57 μA mM – 1 cm – 2 ), low detection limit (1.41 μM), wider linear range (0–3.9 mM) and long–term stability (30 days) have been recorded for electrode thermally oxidized at 400 °C followed by electrochemical reduction process (rCu_400). The sensitivity is almost three times higher in comparison to the planner Cu surface. This significantly enhanced glucose sensing ability rCu_400 has been attributed to the nanofibril morphology, origination of Cu (111) facet and formation of a stable oxide layer evidenced by scanning electron microscopy, X-ray diffraction and energy dispersive spectroscopy analysis. Despite higher sensitivity, rCu_400 electrode does not show any response to the chloride ion, dopamine, ascorbic acid and uric acid. Finally, these results indicate that the Cu nanofibril structure prepared via simple oxidation/reduction process can be an excellent candidate to be used as an electrode for glucose sensing application.

36 MATERIALS SCIENCE↗