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At least 19 records

Process Developed for Generating Ceramic Interconnects With Low Sintering Temperatures for Solid Oxide Fuel Cells

Solid oxide fuel cells (SOFCs) have been considered as premium future power generation devices because they have demonstrated high energy-conversion efficiency, high power density, and extremely low pollution, and have the flexibility of using hydrocarbon fuel. The Solid-State Energy Conversion Alliance (SECA) initiative, supported by the U.S. Department of Energy and private industries, is leading the development and commercialization of SOFCs for low-cost stationary and automotive markets. The targeted power density for the initiative is rather low, so that the SECA SOFC can be operated at a relatively low temperature (approx. 700 C) and inexpensive metallic interconnects can be utilized in the SOFC stack. As only NASA can, the agency is investigating SOFCs for aerospace applications. Considerable high power density is required for the applications. As a result, the NASA SOFC will be operated at a high temperature (approx. 900 C) and ceramic interconnects will be employed. Lanthanum chromite-based materials have emerged as a leading candidate for the ceramic interconnects. The interconnects are expected to co-sinter with zirconia electrolyte to mitigate the interface electric resistance and to simplify the processing procedure. Lanthanum chromites made by the traditional method are sintered at 1500 C or above. They react with zirconia electrolytes (which typically sinter between 1300 and 1400 C) at the sintering temperature of lanthanum chromites. It has been envisioned that lanthanum chromites with lower sintering temperatures can be co-fired with zirconia electrolyte. Nonstoichiometric lanthanum chromites can be sintered at lower temperatures, but they are unstable and react with zirconia electrolyte during co-sintering. NASA Glenn Research Center s Ceramics Branch investigated a glycine nitrate process to generate fine powder of the lanthanum-chromite-based materials. By simultaneously doping calcium on the lanthanum site, and cobalt and aluminum on the chromium site, we could sinter the materials below 1400 C. The doping concentrations were adjusted so that the thermal expansion coefficient matched that of the zirconia electrolyte. Also, the investigation was focused on stoichiometric compositions so that the materials would have better stability. Co-sintering and chemical compatibility with zirconia electrolyte were examined by X-ray diffraction, scanning electron microscopy, and energy dispersive spectroscopy (line scanning and dot map). The results showed that the materials bond well, but do not react, with zirconia electrolyte. The electric conductivity of the materials measured at 900 C in air was about 20 S/cm.

Zhong, Zhi-Min↗

Ceramic Interconnects with Low Sintering Temperature

Ceramic interconnects for use in solid oxide he1 cells are expected to operate between 900 to approximately 1000 C, sinter below 1400 C to allow co-firing and meet a number thermal mechanical requirements. The pervoskite type (ABO3) lanthanum chromite based materials have emerged as a leading candidate that will meet these criteria by varying the composition on the A and B sites. A need therefore exists to determine this material's temperature dependent electrical and mechanical properties with respect to these site substitutions. In this investigation oxide powders were prepared by the glycine-nitrate process. Ionic substitutions were carried out on A sites with Ca or Sr, and B sites with Co and Al, respectively. Only stoichiometric compositions were considered for the sake of stability. The powders and their ability to sinter were investigated by XRD, SEM, dilatometry and density measurements. The sintered materials were further examined by SEM, thermal expansion and electric conductivity measurements in order to elucidate the resulting microstructure, electrical and mechanical properties. In addition quantum mechanical calculations were performed to obtain insight into the effects of these dopants on the materials electronic band structure and lattice parameter.

Zhong, Zhi-Min↗

Advanced Ceramic Technology for Space Applications at NASA MSFC

The ceramic processing technology using conventional methods is applied to the making of the state-of-the-art ceramics known as smart ceramics or intelligent ceramics or electroceramics. The sol-gel and wet chemical processing routes are excluded in this investigation considering economic aspect and proportionate benefit of the resulting product. The use of ceramic ingredients in making coatings or devices employing vacuum coating unit is also excluded in this investigation. Based on the present information it is anticipated that the conventional processing methods provide identical performing ceramics when compared to that processed by the chemical routes. This is possible when sintering temperature, heating and cooling ramps, peak temperature (sintering temperature), soak-time (hold-time), etc. are considered as variable parameters. In addition, optional calcination step prior to the sintering operation remains as a vital variable parameter. These variable parameters constitute a sintering profile to obtain a sintered product. Also it is possible to obtain identical products for more than one sintering profile attributing to the calcination step in conjunction with the variables of the sintering profile. Overall, the state-of-the-art ceramic technology is evaluated for potential thermal and electrical insulation coatings, microelectronics and integrated circuits, discrete and integrated devices, etc. applications in the space program.

Alim, Mohammad A.↗

Effect of processing parameters on the characteristics of high-Tc superconductor YBa2Cu3Oy

SEM, thermogravimetric analysis, powder X-ray diffraction,and measurements of electrical resistivity and magnetic susceptibility, are presently used to characterize the influence of sintering temperature, sintering and annealing atmospheres, and quench-rate on the properties of the YBa2Cu3Oy superconducting oxide. It is established that annealing in oxygen, together with slow cooling rates, are required for preparation of high-Tc superconductors with sharp transitions; rapid quenching from high temperature does not yield good superconductors, due to low oxygen content.

Bansal, Narottam P.↗

Processing effects on the mechanical properties of tungsten heavy alloys

Tungsten heavy alloys exhibit significant mechanical property sensitivities to the fabrication variables. These sensitivities are illustrated in this examination of vacuum sintering and the effects of composition, sintering temperature, and sintering time on the mechanical properties of tungsten heavy alloys. Measurements were conducted to assess the density, strength, hardness, and elongation dependencies. A detrimental aspect of vacuum sintering is matrix phase evaporation, although vacuum sintering does eliminate the need for postsintering heat treatments.

Kishi, Toshihito↗

Powder metallurgy: Solid and liquid phase sintering of copper

Basic powder metallurgy (P/M) principles and techniques are presented in this laboratory experiment. A copper based system is used since it is relatively easy to work with and is commercially important. In addition to standard solid state sintering, small quantities of low melting metals such as tin, zinc, lead, and aluminum can be added to demonstrate liquid phase sintering and alloy formation. The Taguchi Method of experimental design was used to study the effect of particle size, pressing force, sintering temperature, and sintering time. These parameters can be easily changed to incorporate liquid phase sintering effects and some guidelines for such substitutions are presented. The experiment is typically carried out over a period of three weeks.

Sheldon, Rex↗

Processing Techniques Developed to Fabricate Lanthanum Titanate Piezoceramic Material for High-Temperature Smart Structures

Piezoelectric ceramic materials are potential candidates for use as actuators and sensors in intelligent gas turbine engines. For piezoceramics to be applied in gas turbine engines, they will have to be able to function in temperatures ranging from 1000 to 2500 F. However, the maximum use temperature for state-of-the-art piezoceramic materials is on the order of 300 to 400 F. Research activities have been initiated to develop high-temperature piezoceramic materials for gas turbine engine applications. Lanthanum titanate has been shown to have high-temperature piezoelectric properties with Curie temperatures of T(sub c) = 1500 C and use temperatures greater than 1000 C. However, the fabrication of lanthanum titanate poses serious challenges because of the very high sintering temperatures required for densification. Two different techniques have been developed at the NASA Glenn Research Center to fabricate dense lanthanum titanate piezoceramic material. In one approach, lower sintering temperatures were achieved by adding yttrium oxide to commercially available lanthanum titanate powder. Addition of only 0.1 mol% yttrium oxide lowered the sintering temperature by as much as 300 C, to just 1100 C, and dense lanthanum titanate was produced by pressure-assisted sintering. The second approach utilized the same commercially available powders but used an innovative sintering approach called differential sintering, which did not require any additive.

Goldsby, Jon C.↗

Effects of process variables on the properties of YBa2Cu3O(7-x) ceramics formed by investment casting

An investment casting process has been developed to produce net-shape, superconducting ceramics. In this work, a factorial experiment was performed to determine the critical process parameters for producing cast YBa2Cu3O7 ceramics with optimum properties. An analysis of variance procedure indicated that the key variables in casting superconductive ceramics are the particle size distribution and sintering temperature. Additionally, the interactions between the sintering temperature and the other process parameters (e.g., particle size distribution and the use of silver dopants) were also found to influence the density, porosity, and critical current density of the fired ceramics.

Hooker, M. W.↗

Iridium-Doped Ruthenium Oxide Catalyst for Oxygen Evolution

NASA requires a durable and efficient catalyst for the electrolysis of water in a polymer-electrolyte-membrane (PEM) cell. Ruthenium oxide in a slightly reduced form is known to be a very efficient catalyst for the anodic oxidation of water to oxygen, but it degrades rapidly, reducing efficiency. To combat this tendency of ruthenium oxide to change oxidation states, it is combined with iridium, which has a tendency to stabilize ruthenium oxide at oxygen evolution potentials. The novel oxygen evolution catalyst was fabricated under flowing argon in order to allow the iridium to preferentially react with oxygen from the ruthenium oxide, and not oxygen from the environment. Nanoparticulate iridium black and anhydrous ruthenium oxide are weighed out and mixed to 5 18 atomic percent. They are then heat treated at 300 C under flowing argon (in order to create an inert environment) for a minimum of 14 hours. This temperature was chosen because it is approximately the creep temperature of ruthenium oxide, and is below the sintering temperature of both materials. In general, the temperature should always be below the sintering temperature of both materials. The iridium- doped ruthenium oxide catalyst is then fabricated into a PEM-based membrane- electrode assembly (MEA), and then mounted into test cells. The result is an electrolyzer system that can sustain electrolysis at twice the current density, and at the same efficiency as commercial catalysts in the range of 100-200 mA/sq cm. At 200 mA/sq cm, this new system operates at an efficiency of 85 percent, which is 2 percent greater than commercially available catalysts. Testing has shown that this material is as stable as commercially available oxygen evolution catalysts. This means that this new catalyst can be used to regenerate fuel cell systems in space, and as a hydrogen generator on Earth.

Valdez, Thomas I.↗

Effects of oxide additions and temperature on sinterability of milled silicon nitride

Specimens of milled alpha-Si3N4 with 0 to 5.07 equivalent percent of oxide additions were pressureless sintered at 1650 to 1820 C for 4 hours in nitrogen while covered with powdered Si3N4 + SiO2. Densities of less than or equal to 97.5 percent resulted with approximately 2.5 equivalent percent of MgO, CeO2, Y2O3, and three mixtures involving these oxides. Densities of greater than or equal to 94 percent were obtained with approximately 0.62 equivalent percent of the same additives. At most temperatures, best sinterability (density maxima) was obtained with 1.2 to 2.5 equivalent percent additive.

Arias, A.↗

Dynamic porosity variations in ceramics

A silicon carbide disk was sintered from 2090 to 2190 C in 25 C steps. After each sintering step the disk was examined using a precision acoustic scanning system to determine acoustic attenuation and velocity. The bulk density was found to vary nonmonotonically with sintering temperature. During the sintering process, the density varied as much as 10 pct from its value at 2090 C. Local density fluctuations were observed to occur in an organized and history-dependent way. These local density fluctuations varied up to + or - 7 pct of the bulk density and were made visible by acoustic attenuation and velocity mapping.

Generazio, Edward R.↗

Oxygen electrode bifunctional electrocatalyst NiCo2O4 spinel

A significant increase in energy density may be possible if a two-unit alkaline regenerative H2-O2 fuel cell is replaced with a single-unit system that uses passive means for H2O transfer and thermal control. For this single-unit system, new electrocatalysts for the O2 electrode will be required which are not only bifunctionally active but also chemically and electrochemically stable between the voltage range of about 0.7 and 1.5 V. NiCo2O4 spinel is reported to have certain characteristics that make it useful for a study of electrode fabrication techniques. High surface area NiCo2O4 powder was fabricated into unsupported, bifunctional, PTFE-bonded, porous gas fuel cell electrodes by commercial sources using varying PTFE contents and sintering temperatures. The object of this study is to measure the bifunctional activities of these electrodes and to observe what performance differences might result from different commercial electrode fabricators. O2 evolution and O2 reduction data were obtained at 80 C (31 percent KOH). An irreversible reaction (i.e., aging) occurred during O2 evolution at potentials greater than about 1.5 V. Anodic Tafel slopes of 0.06 and 0.12 V/decade were obtained for the aged electrodes. Within the range of 15 to 25 percent, the PTFE content was not a critical parameter for optimizing the electrode for O2 evolution activity. Sintering temperatures between 300 and 340 C may be adequate but heating at 275 C may not be sufficient to properly sinter the PTFE-NiCo2O4 mixture. Electrode disintegration was observed during O2 reduction. Transport of O2 to the NiCo2O4 surface became prohibitive at greater than about -0.02 A/sq cm. Cathodic Tafel slopes of -0.6 and -0.12 V/decade were assumed for the O2 reduction process. A PTFE content of 25 percent (or greater) appears to be preferable for sintering the PTFE-NiCo2O4 mixture.

Fielder, William L.↗

Electrically-nonlinear composite material

Low-temperature sinter of semiconductor and polymer resin is useful in manufacture of circuit boards, cables, and electroexplosive devices. Material can absorb large amounts of heat and can withstand repeated exposures to electrostatic discharges with little deteriorating effects. These characteristics offer significant advantages over high-temperature-sintered, metal-oxide semiconducting materials.

Menichelli, V. J.↗

Ceramic Heat Pipe for Thermal Management of a High Frequency Inductor

As the power density of electric machines and power electronics continues to increase to meet the demands of more electric aircraft, the thermal management of these devices becomes increasingly important. Ideally, the thermal management solution of the device should have high thermal conductivity and be electrically insulating so that it can be directly integrated with the device in question. Technical ceramics are a class of materials that meet these two requirements. Direct liquid cooling by submerging electric components in a dielectric fluid is an alternate option, but adds system complexity and may incur pumping loss. In this work, the thermal management solution for a high frequency inductor is presented. A conventional wicked heat pipe is designed that is made from a solid ceramic case with a sintered ceramic wick. This heat pipe can provide structural support for the core and windings and is electrically insulating, so it does not incur any additional eddy current losses from the high frequency magnetic fields. It does not require additional pumping power, because conventional wicked heat pipes are passive devices. In this paper, the manufacturing process of the ceramic heat pipe is also presented. It is shown that the sintering of large diameter spherical ceramic particles is difficult due to their high specific surface area and low surface free energy. To overcome this difficulty, a flux material was used to initiate liquid phase sintering. The results of the sintering trials show that for the 120 μm diameter α-Al2O3powder selected for the wick, the combination of 1650°C sintering temperature and the addition of 5 wt% talc sintered the porous matrix together sufficiently for use as a heat pipe wic

High-frequency Inductor↗

Ceramic Heat Pipe for Thermal Management of a High Frequency Inductor

As the power density of electric machines and power electronics continues to increase to meet the demands of more electric aircraft, the thermal management of these devices becomes increasingly important. Ideally, the thermal management solution of the device should have high thermal conductivity and be electrically insulating so that it can be directly integrated with the device in question. Technical ceramics are a class of materials that meet these two requirements. Direct liquid cooling by submerging electric components in a dielectric fluid is an alternate option, but adds system complexity and may incur pumping loss. In this work, the thermal management solution for a high frequency inductor is presented. A conventional wicked heat pipe is designed that is made from a solid ceramic case with a sintered ceramic wick. This heat pipe can provide structural support for the core and windings and is electrically insulating, so it does not incur any additional eddy current losses from the high frequency magnetic fields. It does not require additional pumping power, because conventional wicked heat pipes are passive devices. In this paper, the manufacturing process of the ceramic heat pipe is also presented. It is shown that the sintering of large diameter spherical ceramic particles is difficult due to their high specific surface area and low surface free energy. To overcome this difficulty, a flux material was used to initiate liquid phase sintering. The results of the sintering trials show that for the 120 μm diameter α-Al2O3 powder selected for the wick, the combination of 1650°C sintering temperature and the addition of 5 wt% talc sintered the porous matrix together sufficiently for use as a heat pipe wick.

High frequency inductor↗

Preparation and Dielectric Measurements of the Rare Earth Green Phases R2BaCuO(5-x) (R = Y, Sm, Gd, Dy, Ho, Er, Yb)

It has been demonstrated that R2BaCuO(5-x) (R = Y, Sm, Gd, Dy, Ho, Er, Yb) does not undergo significant densification unless the sintering temperatures are near the incongruent melting point or the sintering times are long. Good quality powders of Y2BaCuO(5-x) have been synthesized by using oxide raw materials or precursors such as acetates and nitrates. The acetates- and the nitrates-derived yttrium green phase resulted in finer particle sizes, acceptable dielectric properties and lower melting temperatures than those processed via oxide raw materials. The hot pressing technique has been employed to produce a dense R2BaCuO(5-x) (R=Y,Gd) substrate with satisfactory dielectric properties. Reactivity to reducing conditions, i.e. graphite die, limited the optimization of the properties. A high sensitivity to the annealing atmosphere has been demonstrated in Y2BaCuO,.,,. Oxygen treatment at 950 OC has been shown to improve the dielectric properties while treatment in nitrogen, at the same temperature, degraded desirable properties. A high sensitivity to the annealing atmosphere has been demonstrated in Y2BaCuO(5-x). Oxygen treatment at 950 C has been shown to improve the dielectric properties while treatment in nitrogen, at the same temperature, degraded desirable properties. The dielectric constants of the rare earth green phases R2BaCuO(5-x) were found to be low. Relaxation peaks were detected at low temperatures (T less than 150 K) and at high temperatures (150 less than T greater than 420 K). The dielectric losses and conductivities at 77 K were measured to be in the range of 10(exp -4) and 10(exp -12) (Omega-cm)(exp -1), respectively. Many parameters were found to exhibit dependencies on the rare earth cation sizes.

Gonzalez-Titman, Carlos↗

Effect of oxygen-nitrogen ratio on sinterability of Sialons

The effect of varying the sintering temperature and the oxygen to nitrogen ratio (O/N) on the sinterability of Sialons of the formula Si2.55Al0.6OyN4-0.667y was investigated for y between 0.57 and 1.92 (O/N between 0.157 and 0.706). The Sialons reached maximum density on pressureless sintering for 4 hours at about 1760 C in nitrogen. Optimum sinterability with densities up to about 98 percent of theoretical was attained with negligible X-phase in the O/N range from about 0.2 to 0.3. On sintering at approximately 1830 C the Sialons decomposed with evolution of silicon and aluminum.

Arias, A.↗

Progress in High Power Density SOFC Material Development for Aerospace Applications

Solid oxide fuel cell (SOFC) systems for aircraft applications require order of magnitude increase in specific power density and long life under aircraft operating conditions. Advanced SOFC materials and fabrication processes are being developed at NASA GRC to increase specific power density and durability of SOFC cell and stack. Initial research efforts for increasing specific power density are directed toward increasing the operating temperature for the SOFC system and reducing the weight of the stack. While significant research is underway to develop anode supported SOFC system operating at temperatures in the range of 650 - 850 C for ground power generation applications, such temperatures may not yield the power densities required for aircraft applications. For electrode-supported cells, SOFC stacks with power densities greater than 1.0 W/sq cm are favorable at temperatures in excess of 900 C. The performance of various commercial and developmental anode supported cells is currently being evaluated in the temperature range of 900 to 1000 C to assess the performance gains and materials reliability. The results from these studies will be presented. Since metal interconnects developed for lower temperature operation are not practical at these high temperatures, advanced perovskite based ceramic interconnects with high electronic conductivity and lower sintering temperatures are being developed. Another option for increasing specific power density of SOFC stacks is to decrease the stack weight. Since the interconnect contributes to a significant portion of the stack weight, considerable weight benefits can be derived by decreasing its thickness. Eliminating the gas channels in the interconnect by engineering the pore structure in both anode and cathode can offer significant reduction in thickness of the ceramic interconnect material. New solid oxide fuel cells are being developed with porous engineered electrode supported structures with a 10 - 20 micron thin electrolyte. The performance data for advanced SOFC cells with engineered porosity in both electrodes will be presented.

Cable, Thomas L.↗