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At least 847 records · Page 47

Hafnia-Based Materials Developed for Advanced Thermal/Environmental Barrier Coating Applications

Thermal and environmental barrier coatings (T/EBCs) will play a crucial role in advanced gas turbine engine systems because of their ability to significantly increase engine operating temperatures and reduce cooling requirements, and thus help achieve engine goals of low emissions and high efficiency. Under the NASA Ultra-Efficient Engine Technology (UEET) Project, advanced T/EBCs are being developed for low-emission SiC/SiC ceramic matrix composite (CMC) combustor applications by extending the CMC liner and vane temperature capability to 1650 C (3000 F) in oxidizing and water-vaporcontaining combustion environments. The coating system is required to have increased phase stability, lower lattice and radiation thermal conductivity, and improved sintering and thermal stress resistance under high-heat-flux and thermal-cycling engine conditions. Advanced heat-flux testing approaches (refs. 1 to 4) have been established at the NASA Glenn Research Center for 1650 C coating developments. The simulated combustion water-vapor environment is also being incorporated into the heat-flux test capabilities (ref. 3).

Zhu, Dongming↗

Advanced Oxide Material Systems For 1650 C Thermal/Environmental Barrier Coating Applications

Advanced thermal/environmental barrier coatings (T/EBCs) are being developed for low emission SiC/SiC ceramic matrix composite (CMC) combustor and vane applications to extend the CMC liner and vane temperature capability to 1650 C (3000 F) in oxidizing and water-vapor containing combustion environments. The 1650 C T/EBC system is required to have better thermal stability, lower thermal conductivity, and improved sintering and thermal stress resistance than current coating systems. In this paper, the thermal conductivity, water vapor stability and cyclic durability of selected candidate zirconia-/hafnia-, pyrochlore- and magnetoplumbite-based T/EBC materials are evaluated. The test results have been used to downselect the T/EBC coating materials, and help demonstrate advanced 1650OC coatings feasibility with long-term cyclic durability.

Zhu, Dongming↗

Reactive flash sintering of TiZrN and TiAlN ternary metal nitrides

Here, this study demonstrated the reactive flash sintering (RFS) for two powder mixtures: TiN-ZrN (both conducting) and AlN-TiN (TiN conducting but AlN insulating), targeting ternary metal nitrides (TMN) of Ti 0.5 Zr 0.5 N and Ti 0.5 Al 0.5 N, respectively. A constant volage and pressure (e.g., 8 V DC, ∼15 MPa) at room temperature triggered the flash (current density up to 27 A/mm 2 ) without pre-heating, and the entire RFS process finished in a few minutes. For TiZrN, the flash was instantaneous whereas for TiAlN, there was a long incubation before the flash followed by a quick and dramatic flash. Both conventional ex situ XRD and in situ synchrotron study had been carried out. They showed a uniform Ti 0.57 Zr 0.43 N solution formed in RFS and persisted upon cooling, while (Ti, Al) N solid solution formed at high temperature was not stable and likely went through a very quick phase separation in the cooling process. The final products from RFS had been characterized using SEM/EDS for microstructure. Both TiZrN and TiAlN were dense. Distribution of Ti, Zr, and N was uniform for TiZrN; for TiAlN, Ti and N distribution was uniform, while association of Al with oxygen was observed. TGA-DSC revealed the onset oxidation temperature for TiZrN was comparable to TiN and ZrN, while it was higher by ∼200 °C for TiAlN, likely due to the formation of Al 2 O 3 . In terms of mechanical properties such as hardness or fracture toughness, forming a single-phase solid solution (like TiZrN) does not offer obvious benefits. while large grain size from RFS seemed to be unfavorable. Future optimization of RFS condition and in-depth study by both experiments and simulation are needed to fully understand the composition-processing-structure-property relationships for such TMN from the reactive flash sintering process.

Flash Sintering↗

In situ characterization of ceramic cold sintering by small-angle scattering

The first in situ characterization of the pore morphology evolution during the cold sintering process (CSP) is presented using small-angle X-ray scattering methods. For practical reasons, measurements have been made on a model system, KH 2 PO 4 (KDP). The scattering signal revealed a striking behavior that could be modeled with nanoscale structural features associated with the dissolution and reprecipitation of KDP close to the grain/pore interface during CSP. The prospects for future more quantitative experiments under a range of temperature and pressure conditions, as well as for studies of more technologically important materials such as ZnO are considered.

36 MATERIALS SCIENCE↗

Thermal-Mechanical Analysis of an Additive Manufacturing Ceramic Heat Exchanger for High-Temperature Recuperator in a sCO2 Power System

Supercritical CO2 (sCO2) Brayton power cycle can be configured in a closed-loop power system and has a potentially high cycle efficiency. Compactness and high efficiency of a sCO2 power block make the sCO2 Brayton cycle a versatile power cycle in broad applications. While many heat sources are of sufficient intensity to produce high temperature working fluids to achieve high cycle efficiency, the thermal-mechanical stability of traditional materials (e.g., steels and nickel-based superalloys) used in construction of heat exchangers and turbine components limits the operating conditions and thus thermodynamic efficiency of the system. This effort seeks to establish the viability of ceramic heat exchanger technologies for the most extreme operating conditions envisioned for power generation and other high temperature processes. Heat exchangers constructed from ultra-high temperature ceramics, a class of extreme environment materials featuring melting points (Tmp.) above 3000 degrees C, is particularly appealing for sCO2 Brayton cycles given their ultra-low creep rates and very high retained strength at low homologous temperatures (i.e., T < 0.5 Tmp., or at least 1500 degrees C). To translate these materials properties to ultra-high temperature heat exchangers, innovations are required in ceramic manufacturing techniques to realize the complex architectures featured in compact heat exchangers with high power density. With appropriate processing, ZrB2-SiC based compositions can be sintered to near full density and shaped into complex topologies via ceramic additive manufacturing methods. This paper analyzes heat exchanger designs and explores thermal-mechanical implications of the operating environment. Thermal flow, heat transfer, and conjugate mechanical analyses provide insights into benefits and risks associated with the design approach.

additive manufacturing↗

Pressureless sintered Sialons with low amounts of sintering aid

Two Beta prime - Sialons of composition Si2.6Al0.393y0.007O0.4N3.6 and Si2.6Al0.384Y0.014O0.4N3.6 were pressureless sintered from mixtures of Y2O3 and separately milled Beta -Si3N4, AlN, and SiO2. These Sialons had densities of over 98% of theoretical, four-point bend strengths of 460 and 155 MPa at room temperature and 1400 C, respectively, and 1400 C oxidation rates lower than those reported for hot pressed Si3N4 and for a stronger Sialon with 2.5 weight percentage Y2O3.

Arias, A.↗

Investigation of electrical noise in selenium-immersed thermistor bolometers

The selenium immersed, thermistor bolometer, IR detector failed due to spurious and escalating electrical noise outburst as a function of time at elevated temperatures during routine ground based testing in a space simulated environment. Spectrographic analysis of failed bolometers revealed selenium pure zones in the insulating selenium arsenic (Se-As) glass film which surrounds the active sintered Mn, Ni, Co oxide flake. The selenium pure film was identified as a potentially serious failure mechanism. Significant changes were instituted in the manufacturing techniques along with more stringent process controls which eliminated the selenium pure film and successfully produced 22study bolometers.

Tarpley, J. L.↗

Cell and method for electrolysis of water and anode

An electrolytic cell for converting water vapor to oxygen and hydrogen include an anode comprising a foraminous conductive metal substrate with a 65-85 weight percent iridium oxide coating and 15-35 weight percent of a high temperature resin binder. A matrix member contains an electrolyte to which a cathode substantially inert. The foraminous metal member is most desirably expanded tantalum mesh, and the cell desirably includes reservoir elements of porous sintered metal in contact with the anode to receive and discharge electrolyte to the matrix member as required. Upon entry of a water vapor containing airstream into contact with the outer surface of the anode and thence into contact with iridium oxide coating, the water vapor is electrolytically converted to hydrogen ions and oxygen with the hydrogen ions migrating through the matrix to the cathode and the oxygen gas produced at the anode to enrich the air stream passing by the anode.

Aylward, J. R.↗

Fuzzy sets predict flexural strength and density of silicon nitride ceramics

In this work, we utilize fuzzy sets theory to evaluate and make predictions of flexural strength and density of NASA 6Y silicon nitride ceramic. Processing variables of milling time, sintering time, and sintering nitrogen pressure are used as an input to the fuzzy system. Flexural strength and density are the output parameters of the system. Data from 273 Si3N4 modulus of rupture bars tested at room temperature and 135 bars tested at 1370 C are used in this study. Generalized mean operator and Hamming distance are utilized to build the fuzzy predictive model. The maximum test error for density does not exceed 3.3 percent, and for flexural strength 7.1 percent, as compared with the errors of 1.72 percent and 11.34 percent obtained by using neural networks, respectively. These results demonstrate that fuzzy sets theory can be incorporated into the process of designing materials, such as ceramics, especially for assessing more complex relationships between the processing variables and parameters, like strength, which are governed by randomness of manufacturing processes.

Cios, Krzysztof J.↗

Characterization of NUW-LHT-5m, A Lunar Highland Simulant

A new simulant of the lunar highlands regolith, NUW-LHT-5M, was designed by NASA and manufactured by Washington Mills. The simulant was based on Apollo 16 data and is a member of the NU-LHT-series. NASA’s Marshall Space Flight Center and Johnson Space Center have already purchased 3 metric tons of the simulant for advanced engineering work. In support of engineering uses of the simulant, we provided measurements of the simulant including: mineral abundance and composition, liberation, X-ray fluorescence (XRF), ferrous iron, carbon, sulfur, 60 element inductively coupled plasma (ICP), loss on ignition, particle size, both 2D and 3D particle shape, specific surface area, shear, cohesion, internal friction, helium pycnometry, minimum index density, tap density, magnetic susceptibility, cryogenic and high temperature permittivity, visible and near-infrared (VNIR) and middle infra-red spectroscopy (MIR), differential scanning calorimetry (DSC), viscosity, thermal diffusivity, thermal conductivity, thermal gravimetric analysis (TGA), evolved gas analysis (EGA), and spark sintering. For the crystalline components the design of the simulant called for two rocks from the Stillwater Complex, Montana: 17.6 wt% norite, 37.7% anorthosite, and 4.7 wt% olivine from an unspecified commercial source. The other 40% of the simulant was a high calcium (An100), vesicular glass that Washington Mills made specifically for the simulant. Fabrication and quality control processes for both the glass and the simulant are described. Importantly, most of the graphs and tables presented herein provide values for both the new simulant and data for the older NASA mare simulant, JSC-1A. Finally, we discussed the current limitations of NUW-LT-5M and most other lunar regolith simulants to replicate the lunar material.

lunar regolith simulant↗

High Temperature Protonic Conductors

High Temperature Protonic Conductors (HTPC) with the perovskite structure are envisioned for electrochemical membrane applications such as H2 separation, H2 sensors and fuel cells. Successive membrane commercialization is dependent upon addressing issues with H2 permeation rate and environmental stability with CO2 and H2O. HTPC membranes are conventionally fabricated by solid-state sintering. Grain boundaries and the presence of intergranular second phases reduce the proton mobility by orders of magnitude than the bulk crystalline grain. To enhanced protonic mobility, alternative processing routes were evaluated. A laser melt modulation (LMM) process was utilized to fabricate bulk samples, while pulsed laser deposition (PLD) was utilized to fabricate thin film membranes . Sr3Ca(1+x)Nb(2-x)O9 and SrCe(1-x)Y(x)O3 bulk samples were fabricated by LMM. Thin film BaCe(0.85)Y(0.15)O3 membranes were fabricated by PLD on porous substrates. Electron microscopy with chemical mapping was done to characterize the resultant microstructures. High temperature protonic conduction was measured by impedance spectroscopy in wet air or H2 environments. The results demonstrate the advantage of thin film membranes to thick membranes but also reveal the negative impact of defects or nanoscale domains on protonic conductivity.

Dynys, Fred↗

Novel High Temperature Carbide and Boride Ceramics for Direct Power Extraction Electrode Applications. Final report

The current project aims to develop new carbide and boride ceramic materials that incorporate different metal elements (e.g., (Hf 1-x Zr x )B 2 , also called ceramic solid solutions) and understand the fundamental composition-processing-structure-property relationships for such materials. Specifically, nano powders and related nano-composites for selected mixed metal carbide and boride materials are synthesized from nano-scale mixed precursors obtained from solution-based processing via heat treatment in inert atmosphere. The obtained fine powders were then consolidated into dense ceramics via a novel flash sintering process. The mechanical properties and thermal oxidation resistance for the obtained materials were evaluated for these materials. It was found that different synthesis routes produced powders with somewhat different characteristics in terms of composition and microstructure, which then led to different properties for the final ceramics. The synthesis and processing methods demonstrated in this study might be adopted for developing other similar high temperature ceramics, while the mixed metal or solid solution ceramic materials obtained from this study might be used as hot electrodes for direction power extraction and other energy-related applications.

20 FOSSIL-FUELED POWER PLANTS↗

Optical measurements of soot and temperature profiles in premixed propane-oxygen flames

Two laser diagnostic techniques were used to measure soot volume fractions, number densities and soot particle radii in premixed propane/oxygen flat flames. The two techniques used were two wavelength extinction, using 514.5 nm to 632.8 nm and 457.9 nm to 632.8 nm wavelength combinations, and extinction/scattering using 514.5 nm light. The flames wre fuel-rich (equivalence ratios from 2.1 to 2.8) and had cold gas velocities varying from 3.4 to 5.5 cm/s. Measurements were made at various heights above the sintered-bronze, water-cooled flat flame burner with the equivalence ratio and cold gas velocity fixed. Also, measurements were made at a fixed height above the burner and fixed cold gas velocity while varying the equivalence ratio. Both laser techniques are based on the same underlying assumptions of particle size distribution and soot optical properties. Full Mie theory was used to determine the extinction coefficients K sub ext, and the scattering efficiencies, Q sub vv. Temperature measurements in the flames were made using infrared radiometry. Good agreement between the two techniques in terms of soot particle radii, number density and volume fraction was found for intensity ratios (I/I sub o) between 0.1 and 0.8. For intensity ratios higher or lower than this range, the differences in extinction coefficients at the wavelengths chosen for the two-wavelength method are too small to give accurate results for comparing particle radii and number densities. However, when comparing only soot volume fractions, the agreement between the two techniques continued to be good for intensity ratios up to 0.95.

Lyons, Valerie J.↗

Optical measurements of soot and temperature profiles in premixed propane-oxygen flames

Two laser diagnostic techniques were used to measure soot volume fractions, number densities and soot particle radii in premixed propane/oxygen flat flames. The two techniques used were two wavelength extinction, using 514.5 nm to 632.8 nm and 457.9 nm to 632.8 nm wavelength combinations, and extinction/scattering using 514.5 nm light. The flames were fuel-rich (equivalence ratios from 2.1 to 2.8) and had cold gas velocities varying from 3.4 to 5.5 cm/s. Measurements were made at various heights above the sintered-bronze, water-cooled flat flame burner with the equivalence ratio and cold gas velocity fixed. Also, measurements were made at a fixed height above the burner and fixed cold gas velocity while varying the equivalence ratio. Both laser techniques are based on the same underlying assumptions of particle size distribution and soot optical properties. Full Mie theory was used to determine the extinction coefficients K sub ext, and the scattering efficiencies, Q sub vv. Temperature measurements in the flames were made using infrared radiometry. Good agreement between the two techniques in terms of soot particle radii, number density and volume fraction was found for intensity ratios (I/I sub o) between 0.1 and 0.8. For intensity ratios higher or lower than this range, the differences in extinction coefficients at the wavelengths chosen for the two-wavelength method are too small to give accurate results for comparing particle radii and number densities. However, when comparing only soot volume fractions, the agreement between the two techniques continued to be good for intensity ratios up to 0.95.

Lyons, V. J.↗

Quantification of Swelling in Hematite Pellets Reduced Using Hydrogen–Nitrogen Gas Mixture

Iron ore pellets are reduced in a 50%H 2 –50%N 2 1 atm gas mixture at 750, 800, 850, 900, and 950 °C while simultaneously documenting swelling (change in pellet radius) and weight change. Swelling increases with increasing temperature, with catastrophic swelling (>20% of reduction swelling index) observed at 850, 900, and 950 °C. As the pellet is reduced, the pellet radius increases until 40–50% reduction is achieved, followed by a decrease in diameter beyond 40–50% reduction at 750 and 850 °C. At 950 °C, the pellet radius continues to increase with additional pellet reduction without any subsequent decrease in diameter. Scanning electron microscopy (SEM) analysis shows that the neighboring grains inside the pellet sinter together at 750 and 850 °C, whereas the individual grains sinter internally at 950 °C. SEM analysis and observations suggest that the reduction process at 750 and 850 °C can be approximated as a topochemical reaction process, while the reduction process at 950 °C can no longer be approximated as a topochemical reaction process. In conclusion, an empirical equation for the radius of the pellet is derived with fitting parameters dependent on temperature and the degree of reduction of the pellet undergoing reduction based on the experimental data.

08 HYDROGEN↗

Cr-doped U 3 Si 2 composite fuels under steam corrosion

Dense Cr-doped U 3 Si 2 composite fuels were manufactured by spark plasma sintering, and the effects of Cr addition on mechanical properties and oxidation resistance were investigated. Furthermore, dynamic oxidation testing by thermogravimetric analysis revealed significantly improved oxidation resistance of U 3 Si 2 with minimal doping of 3 wt% Cr. The onset oxidation temperature increased to above 550 °C in air and ~520 °C in steam conditions for the 5 wt% and 10 wt% Cr-doped composites. Steam corrosion testing under 360 °C for 24 hours indicated well-maintained pellet integrity without pulverization for the 10 wt% Cr-doped U 3 Si 2 pellet which only showed minor surface oxidation. The first promising results open up the possibility of designing and manufacturing metal additive-doped U 3 Si 2 composite fuels with significantly-improved corrosion resistance as a potential candidate for accident tolerant fuels.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Constructing high-performance radiation-resistant ternary YSZ-MgO-CNT nanocomposites via tailored nanostructures

Developing long-lifetime bulk-form ceramic-based materials with high irradiation resistance is crucial for advanced nuclear systems. Here, we incorporated carbon nanotubes (CNTs) into yttria-stabilized zirconia (YSZ) and magnesia (MgO) nanocrystals to fabricate bulk YSZ-MgO-CNT nanocomposites with abundant ternary nanostructures by spark plasma sintering. To understand the role of tailored ternary nanostructure on irradiation, we investigated the microstructure and mechanical properties evolutions of the YSZ-MgO-CNT nanocomposites irradiated by multi-energy He + ions at high temperature to different fluences. Compared with the single-phase YSZ and ultrafine-grained YSZ-MgO composites, the YSZ-MgO-CNT nanocomposites possessed higher ability to manage irradiation-induced He bubbles/defects via the defect-interface interactions of proposed “loading-unloading” and “loading-transporting-unloading” mechanisms for controlling the dynamical behaviors of He atoms/defects in the CNT-doped ternary nanostructures, thereby presenting more stable microstructure and better performance in resisting irradiation hardening. In conclusion, this work provides insight into the design of advanced inert matrix nuclear fuel and new nuclear waste management materials.

36 MATERIALS SCIENCE↗

Synthesis Of A Precursor Of Silicon Nitride

Promising route toward production of highly pure, finely divided, easily sinterable silicon nitride (Si3N4) involves thermal decomposition of silicon diimide {Si(NH)2} prepared by ammonolysis of Si(SCN)4 in CH3CN and purified by complete extraction of byproduct NH4SCN by use of ammonia at temperature and pressure above critical point.

Philipp, Warren H.↗