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At least 19 records

A Phenomenological Durability Model for Environmental Barrier Coating Systems Subjected to Steam Oxidation

Environmental barrier coatings (EBC) are used to protect the silicon carbide fiber reinforced silicon carbide matrix (SiC/SiC) ceramic matrix composites (CMC) from rapid surface recession due to volatization by water vapor in a steam oxidation environment. A phenomenological modeling approach is outlined to estimate the durability of a given EBC system when exposed to steam oxidation. The report provides a step-by-step procedure to estimate the life of a given EBC system subjected to thermal loads only. Once calibrated, the methodology can predict the critical thickness of an oxide layer that will cause failure initiation/spallation as well as the remaining strength or stress that the EBC system can take for a given oxide layer thickness

Subodh K Mital

Estimates of Permeability of Water in Rare Earth Silicates Using the Modified Theory of Deal and Grove

The salient elements of the theory of oxide growth under an environmental barrier are reviewed. In addition, the results from steam oxidation tests recently conducted on environmental barrier coated specimens are reported. The oxide thickness between the coating and substrate are reported as a function of time. Also, the results from previously conducted steam oxidation tests are reviewed. An approach to estimate the permeability of water through the various coating systems using the oxide thickness versus time measurements and the theory of oxide growth is demonstrated. Although the steam oxidation tests may have been performed under disparate conditions, the approach allows one to rank the protection efficiency of the various coating systems against substrate oxidation on an equivalent basis.

environmental barrier coatings

Device for steam cladding oxidation testing at TREAT

To compare the chemical degradation of conventional zirconium alloy (Zry) cladding to advance silicon carbide (SiC) cladding in a post loss of coolant accident (LOCA) environment, new nuclear testing capabilities are necessary. The Transient Reactor Test (TREAT) Facility at Idaho National Laboratory (INL) has matured its transient fuel testing capabilities since its 2017 restart. The most recent experiment architecture is the Transient Water Irradiation System in TREAT (TWIST), which is designed to support qualification of accident tolerant fuels in light water reactors. INL has designed and analyzed a natural circulation steam flow modification for TWIST to produce prototypic conditions of cladding oxidation. The in-situ device will be electrically heated to drive natural circulation. Moreover, the SiC cladding requires heating above 1700 °C to observe failure, thus internal prototypic nuclear heating with radiation effects will be used. Thermal hydraulic analysis with RELAP5-3D (Reactor Excursion and Leak Analysis Program) estimated steam fluxes greater than 50 mg cm −2 s −1 can be achieved. These fluxes are adequate to test Zry cladding according to draft regulatory guides and to test SiC cladding according to past experiments.

Oxidation

Current EBC Development and Testing at NASA

SiC SiC Ceramic Matrix Composites (CMCs) are a game changer for advanced power generation equipment because of their high temperature capability, oxidation resistance, and light weight that translate to significant reduction in fuel consumption and emission. Limitations of SiC SiC CMCs include surface recession and component cracking and associated chemical and physical degradation in the CMC. The solution pursued to mitigate surface recession of SiC SiC CMCs is the incorporation of coating systems that provide surface protection, which has become known as an Environmental Barrier Coating (EBC). The development of EBCs for the protection of SiC SiC CMCs was a continuation of coating development work for corrosion protection of silicon-based monolithics. The first and second generation EBCs developed in mid 1990s-early 2000s laid the foundation for current EBCs. Environmental degradation that limits EBC life includes surface recession by steam, oxidation in steam environments, and CMAS-EBC reactions. Many engine tests have been conducted since late 1990s and a first CMC component entered into service in 2016 in a commercial engine. The introduction of CMCs represents significant challenges as failure of the EBC means rapid reduction in component life. A reliable lifing method and engine-relevant testing methods to validate life need to be developed. This paper will current activities on EBC development and testing at NASA.

CMC

C/sic Life Prediction for Propulsion Applications

Accurate life prediction is critical to successful use of ceramic matrix composites (CMC). The tools to accomplish this are immature and not oriented toward the behavior of carbon fiber reinforced silicon carbide (C/SiC), the primary system of interest for many reusable and single mission launch vehicle propulsion and airframe applications. This paper describes an approach and process made to satisfy the need to develop an integrated life prediction system that addresses mechanical durability and environmental degradation of C/SiC. Issues such as oxidation, steam and hydrogen effects on material behavior are discussed. Preliminary tests indicate that steam will aggressively remove SiC seal coat and matrix in line with past experience. The kinetics of water vapor reaction with carbon fibers is negligible at 600 C, but comparable to air attack at 1200 C. The mitigating effect of steam observed in fiber oxidation studies has also been observed in stress rupture tests. Detailed microscopy of oxidized specimens is being carried out to develop the oxidation model. Carbon oxidation kinetics are reaction controlled at intermediate temperatures and diffusion controlled at high temperatures (approximately 1000 C). Activation energies for T-300 and interface pyrolytic carbon were determined as key inputs to the oxidation model. Crack opening as a function of temperature and stress was calculated. Mechanical property tests to develop and verify the probabilistic life model are very encouraging except for residual strength prediction. Gage width is a key variable governing edge oxidation of seal coated specimens. Future efforts will include architectural effects, enhanced coatings, biaxial tests, and LCF. Modeling will need to account for combined effects.

Levine, Stanley R.

C/SIC Life Prediction for Propulsion Applications

Accurate life prediction is critical to successful use of ceramic matrix composites (CMC). The tools to accomplish this are immature and not oriented toward the behavior of carbon fiber reinforced silicon carbide (C/SiC), the primary system of interest for many reusable and single mission launch vehicle propulsion and airframe applications. This paper describes an approach and progress made to satisfy the need to develop an integrated life prediction system that addresses mechanical durability and environmental degradation of C/SiC. Issues such as oxidation, steam and hydrogen effects on material behavior are discussed. Preliminary tests indicate that stream will aggressively remove SiC seal coat and matrix in line with past experience. The kinetics of water vapor reaction with carbon fibers is negligible at 600 C, but comparable to air attack at 1200 C. The mitigating effect of steam observed in fiber oxidation studies has also been observed in stress rupture tests. Detailed microscopy of oxidized specimens is being carried out to develop the oxidation model. Carbon oxidation kinetics are reaction controlled at intermediate temperatures and diffusion controlled at high temperatures (approx. 1000 C). Activation energies for T-300 and interface pyrolytic carbon were determined as key inputs to the oxidation model. Crack opening as a function of temperature and stress was calculated. Mechanical property tests to develop and verify the probabilistic life model are very encouraging except for residual strength prediction. Gage width is a key variable governing edge oxidation of seal coated specimens. Future efforts will include architectural effects, enhanced coatings, biaxial tests, and LCF. Modeling will need to account for combined effects.

Levine, Stanley R.

XPS analysis of molecular contamination and sp 2 amorphous carbon on oxidized (100) diamond

The efficacy of oxygen (O) surface terminations on diamond is an important factor for the performance and stability for diamond-based quantum sensors and electronics. Given the wide breadth of O-termination techniques, it can be difficult to discern which method would yield the highest and most consistent O coverage. Furthermore, the interpretation of surface characterization techniques is complicated by surface morphology and purity, which if not accounted for will yield inconsistent determination of the oxygen coverage. We present a comprehensive approach to consistently prepare and analyze oxygen termination of surfaces on (100) single-crystalline diamond. We report on x-ray photoelectron spectroscopy (XPS) characterization of diamond surfaces treated with six oxidation methods that include various wet chemical oxidation techniques, photochemical oxidation with UV illumination, and steam oxidation using atomic layer deposition (ALD). Our analysis entails a rigorous XPS peak-fitting procedure for measuring the functionalization of O-terminated diamond. The findings herein have provided molecular-level insights on oxidized surfaces in (100) diamond, including the demonstration of clear correlation between the measured oxygen atomic percentage and the presence of molecular contaminants containing nitrogen, silicon, and sulfur. We also provide a comparison of the sp 2 carbon content with the O1s atomic percentage and discern a correlation with the diamond samples treated with dry oxidation which eventually tapers off at a max O1s atomic percentage value of 7.09 ± 0.40%. Given these results, we conclude that the dry oxidation methods yield some of the highest oxygen amounts, with the ALD water vapor technique proving to be the cleanest technique out of all the oxidation methods explored in this work.

XPS

A stable high-humidity bubbler design to supply steam for solid oxide electrolysis cells

A stable steam supply is required for the operation of solid oxide electrolysis cells. Heated water bubblers are the most common method due to the simplicity and inherent safety of the method, however, several design challenges hinder effective implementation. Here, a stable and validated bubbler design is presented, capable of achieving very high steam concentrations, relatively high flow rates, and continuous operation. A piping and instrumentation diagram and bill of materials are provided to enable easy duplication. Critical design parameters are discussed, including safety considerations and materials requirements, which are applicable to any bubbler design. The practical implementation of bubblers is also presented, including methods to prevent condensation instability and reduce backpressure to achieve a stable steam supply. The 3″ x 6″ (7.6 cm × 15.2 cm) bubbler achieves up to 98% steam balance hydrogen at 200 sccm and up to 1 slpm at 96% steam.

08 - HYDROGEN

Accelerated and heterogeneous corrosion of Cr-doped uranium nitride fuel pellets

The steam oxidation of Cr-doped UN fuel pellets is analyzed during sequential isothermal holds up to 720 °C. In situ neutron diffraction results show how Cr is accommodated in a secondary U 2 CrN 3 phase, leading to the formation of a duplex UN/U 2 CrN 3 microstructure. Under corrosion, the oxidation of the two phases begins at 400 °C for UN and 430 °C for U 2 CrN 3 , respectively. Because the UN phase is preferentially oxidized in the presence of U 2 CrN 3 , addition of Cr in UN based nuclear fuel is found to accelerate the corrosion rate. At 430 °C the oxidation of UN in the UN/U 2 CrN 3 microstructure is ~ 5 times faster than pure UN, increasing to ~19 times faster at 460 °C. The oxidation of U 2 CrN 3 produces UO 2 via the formation of two transient intermediate phases. In situ neutron diffraction enables oxidation processes of UN and U 2 CrN 3 components to be followed separately within the two-phase system.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS

Modeling of the Influence of a Damaged Thermally Grown Oxide (TGO) Layer in an Environmental Barrier Coating System

Environmental barrier coatings (EBC) are an enabling technology for the successful application of ceramic matrix composites (CMCs) in air-breathing gas turbine engines. EBCs are susceptible to a number of failure modes including oxidation/delamination, recessions, chemical attack and dissolution, thermomechanical degradation, erosion, and foreign object impact damage in a combustion environment. Spallation of environmental barrier coating (EBC), induced by a thermally grown oxide (TGO) layer, is a key EBC failure mode. The TGO layer, resulting from steam oxidation, grows either from a silicon bond coat layer (if present) or from a silicon carbide (SiC) based substrate itself. The TGO layer evolves (i.e., thickness increases with time) as water vapor and oxygen gradually diffuse through the EBC, and the EBC spalls off once the TGO layer reaches some critical thickness. The critical thickness of the TGO layer for failure is in the range of 20-30 microns, but it can vary due to exposure temperature, microstructure etc. Current work at NASA Glenn Research Center, under the Revolutionary Tools and Methods (RTM) subproject is aimed at addressing associated failure modes in EBC systems and developing robust analysis tools to aid in the design/analysis of these systems. The objective of the current work is to conduct a sensitivity study to examine the influence of uniformly and non-uniformly grown oxide layers on the associated driving forces leading to spallation of the EBC when subjected to isothermal loading. The effect of damage in the TGO layer on the resulting stress states is also assessed both in uniform and non-uniform TGO layers.

Mital, Subodh K.

Influence of Thermally-Grown Oxide (TGO) Layer on the Driving Forces Associated with Failure in Environmental Barrier Coating (EBC) Systems

Environmental barrier coatings (EBC) is an enabling technology for the successful application of ceramic matrix composites (CMCs) in air-breathing gas turbine engines. Spallation of environmental barrier coating (EBC) induced by thermally grown oxide (TGO) layer is a key EBC failure mode. The TGO layer, resulting from steam oxidation, grows either from a silicon bond coat layer (if present) or from the silicon carbide (SiC) based substrate itself. Critical thickness of the TGO layer for failure is in the range of 20-30 microns but it can vary due to exposure temperature, microstructure etc. Current work at NASA Glenn Research Center, under the Revolutionary Tools and Methods (RTM) project is aimed at addressing associated failure modes in EBC systems and developing robust analysis tools to aid in the design/analysis of these systems. The objective of the current work is to conduct a sensitivity study to examine the influence of uniformly and non-uniformly grown oxide layers with or without damage on the associated driving forces leading to spallation of the EBC when subjected to isothermal loading. Initial results indicate that the presence of damage (vertical cracks caused by in-plane stresses) enhances the stresses that are present due to non-uniformity. However, the presence of non-uniformity itself is still the main factor influencing the magnitude of peel and shear stresses in the TGO layer.

Mital, Subodh K.

Modeling of the Influence of Thermally Grown Oxide (TGO) Layers on the Driving Forces in Environmental Barrier Coating Systems

Environmental barrier coatings (EBC) are an enabling technology for the successful application of ceramic matrix composites (CMCs) in air-breathing gas turbine engines. EBCs are susceptible to several failure modes including oxidation/delamination, recession, chemical attack and dissolution, thermomechanical degradation, erosion, and foreign object impact damage in a combustion environment. Spallation of environmental barrier coating (EBC), induced by a thermally grown oxide (TGO) layer, is a key EBC failure mode. The TGO layer, resulting from steam oxidation, grows either from a silicon bond coat layer (if present) or from a silicon carbide (SiC) based substrate itself. The TGO layer evolves (i.e., thickness increases with time) as water vapor and oxygen gradually diffuse through the EBC, and the EBC spalls off once the TGO layer reaches some critical thickness. The critical thickness of the TGO layer for failure is in the range of 20-30 microns, with the actual value depending upon exposure temperature, microstructure, etc. Current work at NASA Glenn Research Center, under the Transformative Tools and Technology (TTT) subproject is aimed at addressing associated failure modes in EBC systems and developing robust analysis tools to aid in the design/analysis of these systems. The objective of the current work is to conduct a sensitivity study to examine the influence of uniformly and non-uniformly grown oxide layers on the associated driving forces leading to spallation of the EBC when subjected to isothermal loading. The effect of damage in the TGO layer on the resulting stress states is also assessed both in uniform and non-uniform TGO layers.

Coatings

The Effect of Oxidation in Environmental Barrier Coatings Subject to Foreign Object Damage

Oxidation and foreign object damage (FOD) are two key failure modes for environmental barrier coatings (EBCs). For EBCs with a silicon (Si) bond coat, a thermally grown oxide (TGO) layer forms at the EBC –bond coat interface. The TGO layer is considered the weak interface, and directly influences the life of the EBC. Moreover, FOD has been shown to cause significant subsurface damage resulting in delamination or spallation of the EBC which can occur at the EBC -bond coat interface or the bond coat -substrate interface. The purpose of this work is to investigate the synergistic effects of oxidation and FOD in a ytterbium disilicate (𝑌𝑏2𝑆𝑖2𝑂7) EBC. FOD testing is conducted on as-deposited and steam oxidized samples at room temperature using a 1.59-mm hardened steel ball projectile. The resulting damage is characterized by optical profilometry and scanning electron microscopy (SEM). Additionally, a quasi-static, mechanical assessment of the EBC bond strength in the presence of a growing TGO is presented.

environmental barrier coatings (EBCs)

Improving anaerobic digestion of sewage sludge to renewable natural gas by the Advanced Pretreatment & Anaerobic Digestion technology (APAD): Pilot testing

Conventional anaerobic digestion (AD) of sewage sludge in wastewater treatment facilities suffers from low carbon conversion efficiency (CCE = 40%) and requires costly CO2 removal for injection of the produced CH4 into the natural gas grid. To address these limitations, we developed the Advanced Pretreatment and Anaerobic Digestion (APAD) process. This integrates Advanced Wet Oxidation & Steam Explosion (AWOEx) pretreatment of residual sludge after conventional AD, followed by biogas upgradation using a novel methanogenic strain, Methanothermobacter wolfeii BSEL, converting CO2 with H2 into CH4 or RNG (renewable natural gas). Pilot-scale results demonstrated that AWOEx pretreatment achieved a CCE of 62% for the residual sludge, 68% higher than the conventional AD process. The CH4 production was further increased by 79%. Subsequent biogas upgrading in a trickling bed reactor with H2 further enhanced total methane output by 100% and resulted in a final CO2 concentration of =3%. The integrated APAD process achieved a remarkable overall CCE of 83%, resulting in a 200% increase in RNG output when compared to conventional AD. Techno-economic analysis revealed that AWOEx pretreatment alone reduced sludge treatment costs from $494 to $253 per ton of dry solids. The complete APAD process incurred a higher cost of treatment of $530 per ton, driven by prices for bottled H2. The process did, however, show gains in energy recovery and decarbonization. Renewable H2, which may reduce in price in the near future, can positively improve the economics of biogas upgrading for the APAD process.

Life Cycle Assessment (LCA)

An Advanced Pretreatment/Anaerobic Digestion (APAD) Technology for Increased Conversion of Sewage Sludge to Bio-natural Gas in Small-scale Wastewater Plants of less than Five tons Sewage Sludge a Day

The problem today of energy production from sewage sludge at small-scale is that conventional Anaerobic Digestion (AD) as used today at Wastewater Treatment Facilities (WWTF) produces too little energy for warrant use of the biogas. It further leaves 50% or more of the waste behind after the treatment. To overcome this problem, we proposed a novel concept based on Advanced Wet Oxidation & Steam Explosion (AWOEx) of the recalcitrant parts of sewage sludge left behind after AD. We further suggest upgrading biogas to renewable natural gas (RNG) using gaseous fermentation of biogas with hydrogen added by a new methanogen. Overall, the DOE funded Advanced Pretreatment & Anaerobic digestion (APAD) project showed significant improvements over current practice. The project demonstrated that AWOEx followed by AD significantly enhanced the carbon conversion efficiency from 37% to 62%, an increase of 68%. This is far higher than the metric for the specific FOA of an increase of 50%. Besides, the project showed high efficiency of our biological conversion of biogas into RNG when using a new isolate of Methanothermobacter wolfeii resulting in a 100% increased production of a refined biogas with maximum 5% CO2. With both AWOEx pretreatment and biogas upgrading, the project showed a CCE of ca. 83%, far higher than any previous work on sewage sludge. Besides over 200% higher amount of energy in the form of RNG, the APAD concept will reduce disposal cost due to significant reduction in the concentration of final sludge product after APAD. The APAD technology can operate as a bolt-on to a conventional AD plant for improving conversion of the residual organics after AD as done in this DOE project. It can further be implemented as a stand-alone process with AWOEx followed by AD for WWTF’s currently operating without AD.

09 BIOMASS FUELS

Growth of a delta-doped silicon layer by molecular beam epitaxy on a charge-coupled device for reflection-limited ultraviolet quantum efficiency

Low-temperature silicon molecular beam epitaxy is used to grow a delta-doped silicon layer on a fully processed charge-coupled device (CCD). The measured quantum efficiency of the delta-doped backside-thinned CCD is in agreement with the reflection limit for light incident on the back surface in the spectral range of 260-600 nm. The 2.5 nm silicon layer, grown at 450 C, contained a boron delta-layer with surface density of about 2 x 10 exp 14/sq cm. Passivation of the surface was done by steam oxidation of a nominally undoped 1.5 nm Si cap layer. The UV quantum efficiency was found to be uniform and stable with respect to thermal cycling and illumination conditions.

Hoenk, Michael E.