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Monolithic Solid Oxide Fuel Cell development

The Monolithic Solid Oxide Fuel Cell (MSOFC) is an oxide-ceramic structure in which appropriate electronic and ionic conductors are fabricated in a honeycomb shape similar to a block of corrugated paperboard. These electronic and ionic conductors are arranged to provide short conduction paths to minimize resistive losses. The power density achievable with the MSOFC is expected to be about 8 kW/kg or 4 kW/L, at fuel efficienceis over 50 percent, because of small cell size and low resistive losses in the materials. The MSOFC operates in the range of 700 to 1000 C, at which temperatures rapid reform of hydrocarbon fuels is expected within the nickel-YSZ fuel channels. Tape casting and hot roll calendering are used to fabricate the MSOFC structure. The performance of the MSOFC has improved significantly during the course of development. The limitation of this system, based on materials resistance alone without interfacial resistances, is 0.093 ohm-sq cm area-specific resistance (ASR). The current typical performance of MSOFC single cells is characterized by ASRs of about 0.4 to 0.5 ohm-sq cm. With further development the ASR is expected to be reduced below 0.2 ohm-sq cm, which will result in power levels greater than 1.4 W/sq cm. The feasibility of the MSOFC concept was proven, and the performance was dramatically improved. The differences in thermal expansion coefficients and firing shrinkages among the fuel cell materials were minimized. As a result of good matching of these properties, the MSOFC structure was successfully fabricated with few defects, and the system shows excellent promise for development into a practical power source.

Myles, K. M.↗

Materials science on parabolic aircraft: The FY 1987-1989 KC-135 microgravity test program

This document covers research results from the KC-135 Materials Science Program managed by MSFC for the period FY87 through FY89. It follows the previous NASA Technical Memorandum for FY84-86 published in August 1988. This volume contains over 30 reports grouped into eight subject areas covering acceleration levels, space flight hardware, transport and interfacial studies, thermodynamics, containerless processing, welding, melt/crucible interactions, and directional solidification. The KC-135 materials science experiments during FY87-89 accomplished direct science, preparation for space flight experiments, and justification for new experiments in orbit.

Curreri, Peter A.↗

Universal Behavior of a Cyclic Oxidation Model

A mathematical model has been generated to represent the iterative, discrete growth and spallation processes associated with cyclic oxidation. Parabolic growth kinetics (k(sub p)) over and a constant spall area (F(sub A)) were assumed, with spalling occurring interfacially at the thickest regions of the scale. Although most models require numerical techniques, the regularity and simplicity of this progression permitted an approximation by algebraic expressions. Normalization could now be performed to reflect all parametric effects, and a universal cyclic oxidation response was generated: W(sub u) = 1/2 {3J(sub u)(sup 1/2)+ J(sub u)(sup 3/2)} where W, is weight change normalized by the maximum and J(sub u) is the cycle number normalized by the number to reach maximum. Similarly, the total amount of metal consumed was represented by a single normalized curve. The factor [(S(sub c)-l)(raised dot)sqrt(F(sub A)k(sub p)DELTAt)] was identified as a general figure of merit, where S(sub c) is the mass ratio of oxide to oxygen and DELTAt is the cycle duration. A cyclic oxidation failure map was constructed, in normalized k(sub p)-F(sub A) space, as defined by the locus of points corresponding to a critical amount of metal consumption in a given time. All three constructions describe behavior for every value of growth rate, spall fraction, and cycle duration by means of single curves, but with two branches corresponding to the times before and after steady state is achieved.

Smialek, James L.↗

Thermal stability relationships between PMR-15 resin and its composites

A study was conducted to investigate the relationship between the thermo-oxidative stability of PMR-15 matrix resin and the stability of graphite-fiber-reinforced composites that contain this resin as the matrix material. Three areas were investigated. The first was the effect of fiber/matrix interfacial bond strength on the isothermal aging weight loss of composites. By using type-A graphite fibers produced by Hercules, it was possible to study composites reinforced with fibers that were processed to receive different surface treatments. One of the fibers was untreated, a second fiber was treated by oxidation to enhance fiber/matrix bonding, and the third type of fiber was coated with an epoxy sizing. These treatments produced three significantly different interfacial bond strengths. The epoxy sizing on the third fiber was quickly oxidized from the bare fiber surfaces at 288, 316, and 343 C. The weight loss due to the removal of the sizing was constant at 1.5 percent. This initial weight loss was not observed in thermo-oxidative stability studies of composites. The PMR-15 matrix satisfactorily protected the reinforcemnt at all three temperatures.

Bowles, Kenneth J.↗

On the shear stabilization of capillary break-up of finite liquid bridges

In this paper we consider an isothermal finite liquid bridge under zero-gravity. A sinusoidal interfacial shear stress drives a nonparallel flow in the bridge. The linear stability of this flow to three-dimensional disturbances (which may deform the cylindrical gas-liquid interface) is determined numerically by solving an elliptic eigenvalue problem. Previous results on shear stabilization of capillary break-up of axially unbounded cylindrical interfaces containing a parallel flow are hereby extended to a nonparallel flow. The turning flow regions influence the stability significantly. However, for the particular cases considered, a small area in parameter space remains where the capillary instability is suppressed through interfacial shear. Second, non-axisymmetric oscillatory instabilities are found which originate from an interaction of the interface deformation and the basic flow. These instabilities may be the isothermal limit of the oscillatory instabilities observed in float-zone crystal growth.

Dijkstra, Henk A.↗

Fluid Physical and Transport Phenomena Studies aboard the International Space Station: Planned Experiments

This paper provides an overview of the microgravity fluid physics and transport phenomena experiments planned for the International Spare Station. NASA's Office of Life and Microgravity Science and Applications has established a world-class research program in fluid physics and transport phenomena. This program combines the vast expertise of the world research community with NASA's unique microgravity facilities with the objectives of gaining new insight into fluid phenomena by removing the confounding effect of gravity. Due to its criticality to many terrestrial and space-based processes and phenomena, fluid physics and transport phenomena play a central role in the NASA's Microgravity Program. Through widely publicized research announcement and well established peer-reviews, the program has been able to attract a number of world-class researchers and acquired a critical mass of investigations that is now adding rapidly to this field. Currently there arc a total of 106 ground-based and 20 candidate flight principal investigators conducting research in four major thrust areas in the program: complex flows, multiphase flow and phase change, interfacial phenomena, and dynamics and instabilities. The International Space Station (ISS) to be launched in 1998, provides the microgravity research community with a unprecedented opportunity to conduct long-duration microgravity experiments which can be controlled and operated from the Principal Investigators' own laboratory. Frequent planned shuttle flights to the Station will provide opportunities to conduct many more experiments than were previously possible. NASA Lewis Research Center is in the process of designing a Fluids and Combustion Facility (FCF) to be located in the Laboratory Module of the ISS that will not only accommodate multiple users but, allow a broad range of fluid physics and transport phenomena experiments to be conducted in a cost effective manner.

Singh, Bhim S.↗

Recent advances in engineering science; Proceedings of the A. Cemal Eringen Symposium, University of California, Berkeley, June 20-22, 1988

Various papers on recent advances in engineering science are presented. Some individual topics addressed include: advances in adaptive methods in computational fluid mechanics, mixtures of two medicomorphic materials, computer tests of rubber elasticity, shear bands in isotropic micropolar elastic materials, nonlinear surface wave and resonator effects in magnetostrictive crystals, simulation of electrically enhanced fibrous filtration, plasticity theory of granular materials, dynamics of viscoelastic media with internal oscillators, postcritical behavior of a cantilever bar, boundary value problems in nonlocal elasticity, stability of flexible structures with random parameters, electromagnetic tornadoes in earth's ionosphere and magnetosphere, helicity fluctuations and the energy cascade in turbulence, mechanics of interfacial zones in bonded materials, propagation of a normal shock in a varying area duct, analytical mechanics of fracture and fatigue.

Koh, Severino L.↗

Conservative Patch Algorithm and Mesh Sequencing for PAB3D

A mesh-sequencing algorithm and a conservative patched-grid-interface algorithm (hereafter Patch Algorithm ) have been incorporated into the PAB3D code, which is a computer program that solves the Navier-Stokes equations for the simulation of subsonic, transonic, or supersonic flows surrounding an aircraft or other complex aerodynamic shapes. These algorithms are efficient, flexible, and have added tremendously to the capabilities of PAB3D. The mesh-sequencing algorithm makes it possible to perform preliminary computations using only a fraction of the grid cells (provided the original cell count is divisible by an integer) along any grid coordinate axis, independently of the other axes. The patch algorithm addresses another critical need in multi-block grid situation where the cell faces of adjacent grid blocks may not coincide, leading to errors in calculating fluxes of conserved physical quantities across interfaces between the blocks. The patch algorithm, based on the Stokes integral formulation of the applicable conservation laws, effectively matches each of the interfacial cells on one side of the block interface to the corresponding fractional cell area pieces on the other side. This approach is comprehensive and unified such that all interface topology is automatically processed without user intervention. This algorithm is implemented in a preprocessing code that creates a cell-by-cell database that will maintain flux conservation at any level of full or reduced grid density as the user may choose by way of the mesh-sequencing algorithm. These two algorithms have enhanced the numerical accuracy of the code, reduced the time and effort for grid preprocessing, and provided users with the flexibility of performing computations at any desired full or reduced grid resolution to suit their specific computational requirements.

Pao, S. P.↗

Delayed Alumina Scale Spallation on Rene'n5+y: Moisture Effects and Acoustic Emission

The single crystal superalloy Rene'N5 (with or without Y-doping and hydrogen annealing) was cyclically oxidized at 1150 C for 1000 hours. After considerable scale growth (>= 500 hours), even the adherent alumina scales formed on Y-doped samples exhibited delayed interfacial spallation during subsequent water immersion tests, performed up to one year after oxidation. Spallation was characterized by weight loss, the amount of spalled area, and acoustic emission response. Hydrogen annealing (prior to oxidation) reduced spallation both before and after immersion, but without measurably reducing the bulk sulfur content of the Y-doped alloys. The duration and frequency of sequential, co-located acoustic emission events implied an interfacial crack growth rate at least 10(exp -3) m/s, but possibly higher than 10(exp 2) m/s. This is much greater than classic moisture-assisted slow crack growth rates in bulk alumina (10(exp -6) to 10(exp -3) m/s), which may still have occurred undetected by acoustic emission. An alternative failure sequence is proposed: an incubation process for preferential moisture ingress leads to a local decrease in interfacial toughness, thus allowing fast fracture driven by stored strain energy.

Smialek, James L.↗

Surface and Interface Properties of PdCr/SiC Schottky Diode Gas Sensor Annealed at 425 C

The surface and interface properties of Pd(0.9)Cr(0.1)/SiC Schottky diode gas sensors both before and after annealing are investigated using Auger Electron Spectroscopy (AES), Scanning Electron Microscopy (SEM), and Energy Dispersive Spectroscopy (EDS). At room temperature the alloy reacted with SiC and formed Pd(x)Si only in a very narrow interfacial region. After annealing for 250 hours at 425 C, the surface of the Schottky contact area has much less silicon and carbon contamination than that found on the surface of an annealed Pd/SiC structure. Palladium silicides (Pd(x)Si) formed at a broadened interface after annealing, but a significant layer of alloy film is still free of silicon and carbon. The chromium concentration with respect to palladium is quite uniform down to the deep interface region. A stable catalytic surface and a clean layer of Pd(0.9)Cr(0.1) film are likely responsible for significantly improved device sensitivity.

Chen, Liang-Yu↗

Surface and Interface Properties of PdCr/SiC Schottky Diode Gas Sensor Annealed at 425 C

The surface and interface properties of Pd(0.9,)Cr(0.1)/SiC Schottky diode gas sensors both before and after annealing are investigated using Auger electron spectroscopy (AES), scanning electron microscopy (SEM), and energy dispersive spectroscopy (EDS). At room temperature the alloy reacted with SiC and formed Pd,Si only in a very narrow interfacial region. After annealing for 250 h ,It 425 C, the surface of the Schottky contact area his much less silicon and carbon contamination than that found on the surface of an annealed Pd/SiC structure. Palladium silicides (Pd(x)Si) formed at a broadened interface after annealing, but a significant layer of alloy film is still free of silicon and carbon. The chromium concentration with respect to palladium is quite uniform down to the deep interface region. A stable catalytic surface and a clean layer of Pd(0.9)Cr(0.1) film are likely responsible for significantly improved device sensitivity.

Chen, Liang-Yu↗

Ultrasonic Characterization of Interfaces in Composite Bonds

The inverse determination of imperfect interfaces from reflection spectra of normal and oblique incident ultrasonic waves in adhesive bonds of multidirectional composites is investigated. The oblique measurements are complicated by the highly dispersed nature of oblique wave spectra at frequencies above 3MHz. Different strategies for bond property reconstruction, including a modulation method, are discussed. The relation of measured interfacial spring density to the physico-chemical model of a composite interface described by polymer molecular bonds to emulate loss of molecular strength on an adhesive composite interface is discussed. This potentially relates the interfacial (adhesion) strength (number of bonds at the adhesive substrate interface) to the spring constant (stiffness) area density (flux), which is an ultrasonically measurable parameter.

Wang, N.↗

Surface and Interface Study of PdCr/SiC Schottky Diode Gas Sensor Annealed at 425 C

The surface and interface properties of Pd(sub 0.9)Cr(sub 0.1/SiC Schottky diode gas sensor both before and after annealing are investigated using Auger Electron Spectroscopy (AES), Scanning Electron Microscopy (SEM), and Energy Dispersive Spectroscopy (EDS). At room temperature the alloy reacted with SiC and formed Pd(sub x)Si only in a very narrow interfacial region. After annealing for 250 hours at 425 deg. C, the surface of the Schottky contact area has much less silicon and carbon contamination than that found on the surface of an annealed Pd/SiC structure. Pd(sub x)Si formed at a broadened interface after annealing, but a significant layer of alloy film is still free of silicon and carbon. The chromium concentration with respect to palladium is quite uniform down to the deep interface region. A stable catalytic surface and a clean layer of Pd(sub 0.9)Cr(sub 0.1) film are likely responsible for significantly improved device sensitivity.

Chen, Liang-Yu↗

Fiber reinforced solids possessing great fracture toughness: The role of interfacial strength

The high tensile strength characteristic of strong interfacial filament/matrix bonding can be combined with the high fracture toughness of weak interfacial bonding, when the filaments are arranged to have alternate sections of high and low shear stress (and low and high toughness). Such weak and strong areas can be achieved by appropriate intermittent coating of the fibers. An analysis is presented for toughness and strength which demonstrates, in broad terms, the effects of varying the coating parameters of concern. Results show that the toughness of interfaces is an important parameter, differences in which may not be shown up in terms of interfacial strength. Some observations are made upon methods of measuring the components of toughness in composites.

Atkins, A. G.↗

Sulfur Impurities and the Microstructure of Alumina Scales

The relationship between the microstructure of alumina scales, adhesion, and sulfur content was examined through a series of nickel alloys oxidized in 1100 to 1200 deg. C cyclic or isothermal exposures in air. In cyclic tests of undoped NiCrAl, adhesion was produced when the sulfur content was reduced, without any change in scale microstructure. Although interfacial voids were not observed in cyclic tests of NiCrAl, they were promoted by long-term isothermal exposures, by sulfur doping, and in most exposures of NiAl. Two single crystal superalloys, PWA 1480 and Rene' N5, were also tested, either in the as-received condition or after the sulfur content had been reduced to less than 1 ppmw by hydrogen annealing. The unannealed alloys always exhibited spalling to bare metal, but interfacial voids were not observed consistently. Desulfurized PWA 1480 and Rene' N5 exhibited remarkable adhesion and no voidage for either isothermal or cyclic exposures. The most consistent microstructural feature was that, for the cases where voids did form, the scale undersides exhibited corresponding areas with ridged oxide grain boundaries. Voids were not required for spallation nor were other microstructural features essential for adhesion. These observations are consistent with the model whereby scale spallation is controlled primarily by interfacial sulfur segregation and the consequent degradation of oxide-metal bonding.

Smialek, James L.↗

Materials Science Experiments on the International Space Station

The Performance Goal for NASA's Microgravity Materials Science Program reads "Use microgravity to establish and improve quantitative and predictive relationships between the structure, processing and properties of materials." The advent of the International Space Station will open up a new era in Materials Science Research including the ability to perform long term and frequent experiments in microgravity. As indicated the objective is to gain a greater understanding of issues of materials science in an environment in which the force of gravity can be effectively switched off. Thus gravity related issues of convection, buoyancy and hydrostatic forces can be reduced and the science behind the structure/processing/properties relationship can more easily be understood. The specific areas of research covered within the program are (1) the study of Nucleation and Metastable States, (2) Prediction and Control of Microstructure (including pattern formation and morphological stability), (3) Phase Separation and Interfacial Stability, (4) Transport Phenomena (including process modeling and thermophysical properties measurement), and (5) Crystal Growth, and Defect Generation and Control. All classes of materials, including metals and alloys, glasses and ceramics, polymers, electronic materials (including organic and inorganic single crystals), aerogels and nanostructures, are included in these areas. The principal experimental equipment available to the materials scientist on the International Space Station (ISS) will be the Materials Science Research Facility (MSRF). Each of these systems will be accommodated in a single ISS rack, which can operate autonomously, will accommodate telescience operations, and will provide real time data to the ground. Eventual plans call for three MSRF racks, the first of which will be shared with the European Space Agency (ESA). Under international agreements, ESA and other partners will provide some of the equipment, while NASA covers launch and integration costs. The MSRF facilities will include modular components, which can be exchanged to provide inserts specifically matched to the engineering requirements of the particular Principal Investigator. To defray costs and avoid duplication of engineering effort NASA is also pursuing the possibility of using facilities provided by international partners. By this means it is anticipated that all of the types of research outlined in the previous paragraph can be done on the ISS.

Gillies, Donald C.↗

The AMOS cell - An improved metal-semiconductor solar cell

A new fabrication process is being developed which significantly improves the efficiency of metal-semiconductor solar cells. The resultant effect, a marked increase in the open-circuit voltage, is produced by the addition of an interfacial layer oxide on the semiconductor. Cells using gold on n-type gallium arsenide have been made in small areas (0.17 sq cm) with conversion efficiencies of 15% in terrestrial sunlight.

Stirn, R. J.↗

Tribological properties of boron nitride synthesized by ion beam deposition

The adhesion and friction behavior of boron nitride films on 440 C bearing stainless steel substrates was examined. The thin films containing the boron nitride were synthesized using an ion beam extracted from a borazine plasma. Sliding friction experiments were conducted with BN in sliding contact with itself and various transition metals. It is indicated that the surfaces of atomically cleaned BN coating film contain a small amount of oxides and carbides, in addition to boron nitride. The coefficients of friction for the BN in contact with metals are related to the relative chemical activity of the metals. The more active the metal, the higher is the coefficient of friction. The adsorption of oxygen on clean metal and BN increases the shear strength of the metal - BN contact and increases the friction. The friction for BN-BN contact is a function of the shear strength of the elastic contacts. Clean BN surfaces exhibit relatively strong interfacial adhesion and high friction. The presence of adsorbates such as adventitious carbon contaminants on the BN surfaces reduces the shear strength of the contact area. In contrast, chemically adsorbed oxygen enhances the shear strength of the BN-BN contact and increases the friction.

Miyoshi, K.↗