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At least 307 records · Page 17

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.↗

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.↗

Preparation and evaluation of silicon nitride matrices for silicon nitride-SiC fiber composites

Continuous silicon carbide (SiC) fiber was added to three types of silicon nitride (Si3N4) matrices. Efforts were aimed at producing a dense Si3N4 matrix from reaction-bonded silicon nitride (RBSN) by hot-isostatic-pressing (HIP) and pressureless sintering, and from Si3N4 powder by hot-pressing. The sintering additives utilized were chosen to allow for densification, while not causing severe degradation of the fiber. The ceramic microstructures were evaluated using scanning optical microscopy. Vickers indentation was used to determine the microhardness and fracture toughness values of the matrices. The RBSN matrices in this study did not reach more than 80 percent of theoretical density after sintering at various temperatures, pressures, and additive levels. Hot-pressing Si3N4 powder produced the highest density matrices; hardness and toughness values were within an order of magnitude of the best literature values. The best sintering aid composition chosen included Y2O3, SiO2, and Al2O3 or AlN. Photomicrographs demonstrate a significant reduction of fiber attack by this additive composition.

Axelson, Scott R.↗

Evaluation and ranking of candidate ceramic wafer engine seal materials

Modern engineered ceramics offer high temperature capabilities not found in even the best superalloy metals. The high temperature properties of several selected ceramics including aluminum oxide, silicon carbide, and silicon nitride are reviewed as they apply to hypersonic engine seal design. A ranking procedure is employed to objectively differentiate among four different monolithic ceramic materials considered, including: a cold-pressed and sintered aluminum oxide; a sintered alpha-phase silicon carbide; a hot-isostatically pressed silicon nitride; and a cold-pressed and sintered silicon nitride. This procedure is used to narrow the wide range of potential ceramics considered to an acceptable number for future detailed and costly analyses and tests. The materials are numerically scored according to their high temperature flexural strength; high temperature thermal conductivity; resistance to crack growth; resistance to high heating rates; fracture toughness; Weibull modulus; and finally according to their resistance to leakage flow, where materials having coefficients of thermal expansion closely matching the engine panel material resist leakage flow best. The cold-pressed and sintered material (Kyocera SN-251) ranked the highest in the overall ranking especially when implemented in engine panels made of low expansion rate materials being considered for the engine, including Incoloy and titanium alloys.

Steinetz, Bruce M.↗

Non-destructive, ultra-low resistance, thermally stable contacts for use on shallow junction InP solar cells

Contact formation to InP is plagued by violent metal-semiconductor intermixing that takes place during the contact sintering process. Because of this the InP solar cell cannot be sintered after contact deposition. This results in cell contact resistances that are orders of magnitude higher than those that could be achieved if sintering could be performed in a non-destructive manner. We report here on a truly unique contact system involving Au and Ge, which is easily fabricated, which exhibits extremely low values of contact resistivity, and in which there is virtually no metal-semiconductor interdiffusion, even after extended sintering. We present a description of this contact system and suggest possible mechanisms to explain the observed behavior.

Weizer, V. G.↗

The structural and electrical properties of low-resistance Ni contacts to InP

We have investigated the electrical and metallurgical behavior of the Ni-InP contact system. Specific contact resistivity (Rc) values in the low 10 exp -7 Omega-sq cm range are achieved with Ni-only contacts on n-InP by sintering at 400 C for several minutes. The postsinter contact metallization consists of three layers, arranged in the sequence: InP/Ni3P/Ni2P/In. Extended sintering (40 min) at 400 C brings about a rise in Rc to the 10 exp -4 Omega-sq cm range. After extended sintering, the contact metallization is found to consist of only two layers, arranged in the sequence: InP/Ni2P/In. Based on the correlation between low Rc and the presence of Ni3P at the metal-InP interface, it is suggested that the presence of Ni3P is the cause of the low Rc values. We show that the sintering schedule used to achieve low values of Rc is accompanied by substantial metal-InP interdiffusion that results in severe device degradation.

Fatemi, Navid S.↗

Corrosion Issues for Ceramics in Gas Turbines

The requirements for hot-gas-path materials in gas turbine engines are demanding. These materials must maintain high strength and creep resistance in a particularly aggressive environment. A typical gas turbine environment involves high temperatures, rapid gas flow rates, high pressures, and a complex mixture of aggressive gases. Figure 26.1 illustrates the requirements for components of an aircraft engine and critical issues [1]. Currently, heat engines are constructed of metal alloys, which meet these requirements within strict temperature limits. In order to extend these temperature limits, ceramic materials have been considered as potential engine materials, due to their high melting points and stability at high temperatures. These materials include oxides, carbides, borides, and nitrides. Interest in using these materials in engines appears to have begun in the 1940s with BeO-based porcelains [2]. During the 1950s, the efforts shifted to cermets. These were carbide-based materials intended to exploit the best properties of metals and ceramics. During the 1960s and 1970s, the silicon-based ceramics silicon carbide (SiC) and silicon nitride (Si3N4) were extensively developed. Although the desirable high-temperature properties of SiC and Si3N4 had long been known, consolidation of powders into component-sized bodies required the development of a series of specialized processing routes [3]. For SiC, the major consolidation routes are reaction bonding, hot-pressing, and sintering. The use of boron and carbon as additives which enable sintering was a particularly noteworthy advance [4]. For Si3N4 the major consolidation routes are reaction bonding and hot pressing [5]. Reaction-bonding involves nitridation of silicon powder. Hot pressing involves addition of various refractory oxides, such as magnesia (MgO), alumina (Al2O3), and yttria (y2O3). Variations on these processes include a number of routes including Hot Isostatic Pressing (HIP), gas-pressure sintering, sinter-HIPing, and Encapsulation-HIPing. It is important to note that each process involves the addition of secondary elements, which later were shown to dramatically influence oxidation and corrosion behavior. As dense bodies of silicon-based ceramics became more readily available, their desirable high temperature properties were confirmed. These materials retained strength to very high temperatures (i.e. 1300-1400 C). Further, they were lightweight and made from abundant materials. SiC and Si3N4 therefore emerged as leading ceramic candidates for components in heat engines, designed to operate at higher temperatures for better performance and fuel efficiency. The first US programs for ceramics in heat engines have been reviewed [6]. Selected programs on ceramic engine parts are summarized here in regard to their contributions to understanding the corrosion behavior of a heat engine environment.

Jacobson, Nathan S.↗

Fossilization Processes in Thermal Springs

To create a comparative framework for the study of ancient examples, we have been carrying out parallel studies of the microbial biosedimentology, taphonomy and geochemistry of modem and sub-Recent thermal spring deposits. One goal of the research is the development of integrated litho- and taphofacies models for siliceous and travertline sinters. Thermal springs are regarded as important environments for the origin and early evolution of life on Earth, and we seek to utilize information from the fossil record to reconstruct the evolution of high temperature ecosystems. Microbial contributions to the fabric of thermal spring sinters occur when population growth rates keep pace with, or exceed rates of inorganic precipitation, allowing for the development of continuous biofilms or mats. In siliceous thermal springs, microorganisms are typically entombed while viable. Modes of preservation reflect the balance between rates of organic matter degradation, silica precipitation and secondary infilling. Subaerial sinters are initially quite porous and permeable and at temperatures higher than about 20 C, organic materials are usually degraded prior to secondary infilling of sinter frameworks. Thus, organically-preserved microfossils are rare and fossil information consists of characteristic biofabrics formed by the encrustation and underplating of microbial mat surfaces. This probably accounts for the typically low total organic carbon values observed in thermal spring deposits. In mid-temperature, (approx. 35 - 59 C) ponds and outflows, the surface morphology of tufted Phormidium mats is preserved through mat underplating by thin siliceous: crusts. Microbial taxes lead to clumping of ceils and/or preferred filament orientations that together define higher order composite fabrics in thermal spring stromatolites (e.g. network, coniform, and palisade). At lower temperatures (less than 35 C), Calothrix mats cover shallow terracette pools forming flat carpets or pustular surfaces that produce palisade and "shrub" fabrics, respectively. At finer scales, composite fabrics are seen to consist distinctive associations of microstructures formed by the encrustation of individual cells and filaments. Composite fabrics survive the diagenetic transitions from primary opaline silica to quartz and are known from subaerial thermal spring deposits as old as Lower Carboniferous. However, fossil microorganisms tend to be rare in older deposits, and are usually preserved only where cells or sheaths have been stained by iron oxides. In subaqueous mineralizing springs at lower temperatures, early infilling leads to a more rapid and complete reduction in porosity and permeability. This process, along with the slower rates of microbial degradation at lower temperatures, creates a more favorable situation for organic matter preservation. Application of this taphonomic model to the Rhynie Chert, previously interpreted as subaerial, suggest it was probably deposited in a subaqueous spring setting at lower temperatures.

Farmer, Jack D.↗

Pulsed Laser Deposition of BaCe(sub 0.85)Y(sub 0.15)0(sub 3) FILMS

Pulsed laser deposition has been used to grow nanostructured BaCe(sub 0.85)Y(sub 0.15)0(sub 3) films. The objective is to enhance protonic conduction by reduction of membrane thickness. Sintered samples and laser targets were prepared by sintering BaCe(sub 0.85)Y(sub 0.15)O(sub 3) powders derived by solid state synthesis. Films 2 to 6 m thick were deposited by KrF excimer laser on Si and porous Al2O3 substrates. Nanocrystalline films were fabricated at deposition temperatures of 600-800 C deg at O2 pressure of 30 mTorr and laser fluence of 1.2 J/cm square. Films were characterized by x-ray diffraction, scanning electron microscopy and electrical impedance spectroscopy. Dense single phase BaCe(sub 0.85)Y((sub 0.15) 0(sub 3) films with a columnar growth morphology is observed, preferred crystal growth was found to be dependent upon deposition temperature and substrate type. Electrical conductivity of bulk samples produced by solid state sintering and thin film samples were measured over a temperature range of 100 C deg to 900 C deg in moist argon. Electrical conduction of the fabricated films was 1 to 4 orders of magnitude lower than the sintered bulk samples. With respect to the film growth direction, activation energy for electrical conduction is 3 times higher in the perpendicular direction than the parallel direction.

Dynys, F. W.↗

Method for fabricating ceramic filaments and high density tape casting method

An apparatus and method is disclosed for fabricating mats of ceramic material comprising preparing a slurry of ceramic particles in a binder/solvent, charging the slurry into a vessel, forcing the slurry from the vessel into spinneret nozzles, discharging the slurry from the nozzles into the path of airjets to enhance the sinuous character of the slurry exudate and to dry it, collecting the filaments on a moving belt so that the filaments overlap each other thereby forming a mat, curing the binder therein, compressing and sintering the mat to form a sintered mat, and crushing the sintered mat to produce filament shaped fragments. A process is also disclosed for producing a tape of densely packed, bonded ceramic particles comprising forming a slurry of ceramic particles and a binder/solvent, applying the slurry to a rotating internal molding surface, applying a large centrifugal force to the slurry to compress it and force excess binder/solvent from the particles, evaporating solvent and curing the binder thereby forming layers of bonded ceramic particles and cured binder, and separating the binder layer from the layer of particles. Multilayers of ceramic particles are cast in an analogous manner on top of previously formed layers. When all of the desired layers have been cast the tape is fired to produce a sintered tape. For example, a three-layer tape is produced having outer layers of highly compressed filament shaped fragments of strontium doped lanthanum (LSM) particles and a center layer of yttria stabilized zicronia (YSZ) particles.

Collins, Jr., Earl R.↗

High Thermal Conductivity NARloy-Z-Diamond Composite Combustion Chamber Liner For Advanced Rocket Engines

Advanced high thermal conductivity materials research conducted at NASA Marshall Space Flight Center (MSFC) with state of the art combustion chamber liner material NARloy-Z showed that its thermal conductivity can be increased significantly by adding diamond particles and sintering it at high temperatures. For instance, NARloy-Z containing 40 vol. percent diamond particles, sintered at 975C to full density by using the Field assisted Sintering Technology (FAST) showed 69 percent higher thermal conductivity than baseline NARloy-Z. Furthermore, NARloy-Z-40vol. percent D is 30 percent lighter than NARloy-Z and hence the density normalized thermal conductivity is 140 percent better. These attributes will improve the performance and life of the advanced rocket engines significantly. By one estimate, increased thermal conductivity will directly translate into increased turbopump power up to 2X and increased chamber pressure for improved thrust and ISP, resulting in an expected 20 percent improvement in engine performance. Follow on research is now being conducted to demonstrate the benefits of this high thermal conductivity NARloy-Z-D composite for combustion chamber liner applications in advanced rocket engines. The work consists of a) Optimizing the chemistry and heat treatment for NARloy-Z-D composite, b) Developing design properties (thermal and mechanical) for the optimized NARloy-Z-D, c) Fabrication of net shape subscale combustion chamber liner, and d) Hot fire testing of the liner for performance. FAST is used for consolidating and sintering NARlo-Z-D. The subscale cylindrical liner with built in channels for coolant flow is also fabricated near net shape using the FAST process. The liner will be assembled into a test rig and hot fire tested in the MSFC test facility to determine performance. This paper describes the development of this novel high thermal conductivity NARloy-Z-D composite material, and the advanced net shape technology to fabricate the combustion chamber liner. Properties of optimized NARloy-Z-D composite material will also be presented.

Bhat, Biliyar N.↗

Homogeneity Study of ZrC, NbC, and TaC Binary Carbide Fuels for the Application of Nuclear Thermal Propulsion

In alignment with NASA and DARPA goals, efforts towards Nuclear Thermal Propulsion (NTP) have increased in recent years. As progress is made, a main challenge still exists; the fuel in an NTP system must survive the extreme environment experienced during operating conditions. Three fuel forms have been studied including a ceramic-metallic matrix, a ceramic-ceramic matrix, and solid solution carbides. Solid solution carbides were studied previously as a fuel for NTP and was shown to be a promising technology; however, the programs were canceled before demonstration in an NTP engine test. Of the refractory metal carbides of interest, zirconium carbide (ZrC), niobium carbide (NbC) and tantalum carbide (TaC) were studied. ZrC, NbC, and TaC powders were consolidated in monocarbide (ZrC, NbC, TaC) and bi-carbide (ZrC-NbC, ZrC-TaC, NbC-TaC) forms using spark plasma sintering (SPS), with 50-50 mol% compositions of the bi-carbides of interest. The time and temperature conditions to achieve a completely homogeneous solid solution for the mixed carbides is of interest for NTP fuel applications, since this homogeneity is considered to be essential for this fuel form. Homogeneity is typically not achieved during sintering, as surface diffusion (predominant for sintering to near ideal density) tends to occur at lower temperatures than bulk volumetric diffusion (required for solute interdiffusion to achieve a homogeneous solid solution). High temperature isochronal annealing was performed to identify the conditions to achieve a chemically homogeneous sample. The solute interpenetration vs annealing temperature was quantified using energy dispersion spectroscopy (EDS) in a scanning electron microscope (SEM). X-ray diffraction (XRD) was used to accurately measure the phase stability and lattice parameter as a function of annealing conditions. The diffusion data from each sample was then used to determine self-diffusion coefficients for interdiffusion of the Nb, Zr, and Ta solutes and compared to existing literature values. The minimum annealing conditions to achieve complete chemical homogeneity for each carbide was determined.

nuclear thermal propulsion↗

Preparation and evaluation of thin-film sodium tungsten bronzes

Thin films of sodium tungsten bronze (NaxWO3) were investigated as reversible sodium ion electrodes for solid electrolytes. The films were made by electron beam evaporation of the three phases, W metal, Na2WO4, and WO3, followed by sintering. The substrates were sodium beta alumina disks and glass slides. X-ray diffraction analyses of the films showed that sintering in dry nitrogen with prior exposure to air lead to mixed phases. Sintering in vacuum with no air exposure produced tetragonal I bronze with a nominal composition of Na0.31WO3, single phase within the limits of X-ray diffraction detectability. The films were uniform and adherent on sodium beta alumina substrates. The ac and dc conductivities of the beta alumina were measured with the sodium tungsten bronze films as electrodes. These experiments indicated that the tetragonal I bronze electrodes were not completely reversible. This may have resulted from sodium ion blocking within the bronze film or at the bronze beta alumina interface. Methods for attempting to make more completely reversible electrodes are suggested.

Kautz, H. E.↗

Method of electroforming a rocket chamber

A transpiration cooled rocket chamber is made by forming a porous metal wall on a suitably shaped mandrel. The porous wall may be made of sintered powdered metal, metal fibers sintered on the mandrel or wires woven onto the mandrel and then sintered to bond the interfaces of the wires. Intersecting annular and longitudinal ribs are then electroformed on the porous wall. An interchamber wall having orifices therein is then electroformed over the annular and longitudinal ribs. Parallel longitudinal ribs are then formed on the outside surface of the interchamber wall after which an annular jacket is electroformed over the parallel ribs to form distribution passages therewith. A feed manifold communicating with the distribution passages may be fabricated and welded to the rocket chamber or the feed manifold may be electroformed in place.

Fortini, A.↗

A study of degradation of plates for nickel-cadmium spacecraft cells

The relative merits of coining and not coining of sintered nickel oxide and cadmium plates was investigated. Sample plate materials from most commercial cell suppliers were obtained and characterized for properties that may correlate with the tendency toward physical disintegration during handling and over long periods of time in the cell. Special test methods were developed to obtain comparative data in a short time. A wide range of physical properties and coining thickness was observed, resulting in a range of responses. The stronger materials resisted loss of sinter better than weaker materials whether or not coined. Coining improved handling and resistance to electrochemical cycling of weaker materials. The mechanism of break-down of positive plate edges under cycling appears to be the same as that of thickening and blistering. Brittle, nonadherent sinter, resulting from certain impregnation processes, is the most vulnerable to degradation. It is concluded that the latter type of materials should be coined, but coining of strong materials is optional.

Scott, W. R.↗

Improved performance of silicon nitride-based high temperature ceramics

Recent progress in the production of Si3N4 based ceramics is reviewed: (1) high temperature strength and toughness of hot pressed Si3N4 were improved by using high purity powder and a stabilized ZrO2 additive, (2) impact resistance of hot pressed Si3N4 was increased by the use of a crushable energy absorbing layer, (3) the oxidation resistance and strength of reaction sintered Si3N4 were increased by impregnating reaction sintered silicon nitride with solutions that oxidize to Al2O3 or ZrO2, (4) beta prime SiA1ON compositions and sintering aids were developed for improved oxidation resistance or improved high temperature strength.

Ashbrook, R. L.↗

Formation of porous surface layers in reaction bonded silicon nitride during processing

An effort was undertaken to determine if the formation of the generally observed layer of large porosity adjacent to the as-nitride surfaces of reaction bonded silicon nitrides could be prevented during processing. Isostatically pressed test bars were prepared from wet vibratory milled Si powder. Sintering and nitriding were each done under three different conditions:(1) bars directly exposed to the furnance atmosphere; (2) bars packed in Si powder; (3) bars packed in Si3N4 powder. Packing the bars in either Si of Si3N4 powder during sintering retarded formation of the layer of large porosity. Only packing the bars in Si prevented formation of the layer during nitridation. The strongest bars (316 MPa) were those sintered in Si and nitrided in Si3N4 despite their having a layer of large surface porosity; failure initiated at very large pores and inclusions. The alpha/beta ratio was found to be directly proportional to the oxygen content; a possible explanation for this relationship is discussed.

Shaw, N. J.↗

Effect of W and WC on the oxidation resistance of yttria-doped silicon nitride

The effect of W and WC contamination on the oxidation and cracking in air of sintered Si3N4 - 8 w/o Y2O3 ceramics at 500, 750, and 1350 C is examined. A mixture of Si3N4 - 8Y2O3, milled with alumina balls, was divided into four portions. Three portions were doped with 2 w/o WC W, and 4 w/o W respectively, in order to simulate contamination during milling. The fourth portion was undoped and used on a control. The addition of W or WC did not affect the phase relationships in the system, as all bars with or without additions contained melilite as the major Si-Y-O-N phase after sintering. At 750 C, instability (rapid oxidation and cracking) of W-doped bars appears to have occurred as a result of oxidation of the tungsten containing melilite phase. No intermediate temperature instability was observed in bars containing 2 w/o WC or in bars with no additive. Specimens exposed at 1350 C had good oxidation resistance due to the formation of a protective siliceous oxide layer. A specimen containing 4 w/o W which was preoxidized at 1350 C had improved oxidation resistance at 750 C. The tendency towards oxidation and cracking of Si3N4 - 8 Y2O3 at 750 C is concluded to be related to tungsten content of the sintered bars.

Schuon, S.↗