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NASA NTRS1981

Cathode catalysts for primary phosphoric acid fuel cells

Alkylation or carbon Vulcan XC-72, the support carbon, was shown to provide the most stable bond type for linking cobalt dehydrodibenzo tetraazannulene (CoTAA) to the surface of the carbon; this result is based on data obtained by cyclic voltammetry, pulse voltammetry and by release of 14C from bonded CoTAA. Half-cell tests at 100 C in 85% phosphoric acid showed that CoTAA bonded to the surface of carbon (Vulcan XC-72) via an alkylation procedure is a more active catalyst than is platinum based on a factor of two improvement in Tafel slope; dimeric CoTAA had catalytic activity equal to platinum. Half-cell tests also showed that bonded CoTAA catalysts do not suffer a loss in potential when air is used as a fuel rather than oxygen. Commercially available polytetrafluroethylene (PTFE) was shown to be unstable in the fuel cell environment with degradation occurring in 2000 hours or less. The PTFE was stressed at 200 C in concentrated phosphoric acid as well as electrochemically stressed in 150 C concentrated phosphoric acid; the surface chemistry of PTFE was observed to change significantly. Radiolabeled PTFE was prepared and used to verify that such chemical changes also occur in the primary fuel cell environment.

Source record↗

NASA NTRS1980

Cathode catalyst for primary phosphoric fuel cells

Alkylation of Vulcan XC-72 provided the most stable bond type for linking CoTAA to the surface of the carbon; this result is based on data obtained by cyclic voltammetry, pulse voltammetry and by release of 14C from bonded CoTAA. Half-cell tests at 100 C in 85% phosphoric acid showed that CoTAA bonded to the surface of carbon (Vulcan XC-72) via an alkylation procedure is a more active catalyst than is platinum based on a factor of two improvement in Tafel slope; dimeric CoTAA has catalytic activity equal to platinum. Half-cell tests also showed that bonded CoTAA catalysts do not suffer a loss in potential when air is used as a fuel rather than oxygen. Commercially available PTFE was shown to be stable for four months in 200 C 85% phosphoric acid based on lack of change in surface wetting properties, IR and physical characteristics. When stressed electrochemically in 150 C 85% phosphoric acid, PTFE also showed no changes after one month.

Walsh, F.↗

NASA NTRS1981

Ultraviolet /UV/ sensitive phosphors for silicon imaging detectors

The fluorescence properties of UV sensitive organic phosphors and the radiometric properties of phosphor coated silicon detectors in the VUV, UV, and visible wavelengths are described. With evaporated films of coronene and liumogen, effective quantum efficiencies of up to 20% have been achieved on silicon photodiodes in the vacuum UV. With thin films of methylmethacrylate (acrylic), which are doped with organic laser dyes and deposited from solution, detector quantum efficiencies of the order of 15% for wavelengths of 120-165 nm and of 40% for wavelengths above 190 nm have been obtained. The phosphor coatings also act as antireflection coatings and thereby enhance the response of coated devices throughout the visible and near IR.

Viehmann, W.↗

NASA NTRS1990

Laser-induced fluorescence of phosphors for remote cryogenic thermometry

Remote cryogenic temperature measurements can be made by inducing fluorescence in phosphors with temperature-dependent emissions and measuring the emission lifetimes. The thermographic phosphor technique can be used for making precision, noncontact, cryogenic-temperature measurements in electrically hostile environments, such as high dc electric or magnetic fields. The National Aeronautics and Space Administration is interested in using these thermographic phosphors for mapping hot spots on cryogenic tank walls. Europium-doped lanthanum oxysulfide (La2O2S:Eu) and magnesium fluorogermanate doped with manganese (Mg4FGeO6:Mn) are suitable for low-temperature surface thermometry. Several emission lines, excited by a 337-nm ultraviolet laser, provide fluorescence lifetimes having logarithmic dependence with temperature from 4 to above 125 K. A calibration curve for both La2O2S:Eu and Mg4FGeO6:Mn is presented, as well as emission spectra taken at room temperature and 11 K.

Beshears, D. L.↗

NASA NTRS1991

Surface temperature/heat transfer measurement using a quantitative phosphor thermography system

A relative-intensity phosphor thermography technique developed for surface heating studies in hypersonic wind tunnels is described. A direct relationship between relative emission intensity and phosphor temperature is used for quantitative surface temperature measurements in time. The technique provides global surface temperature-time histories using a 3-CCD (Charge Coupled Device) video camera and digital recording system. A current history of technique development at Langley is discussed. Latest developments include a phosphor mixture for a greater range of temperature sensitivity and use of castable ceramics for inexpensive test models. A method of calculating surface heat-transfer from thermal image data in blowdown wind tunnels is included in an appendix, with an analysis of material thermal heat-transfer properties. Results from tests in the Langley 31-Inch Mach 10 Tunnel are presented for a ceramic orbiter configuration and a four-inch diameter hemisphere model. Data include windward heating for bow-shock/wing-shock interactions on the orbiter wing surface, and a comparison with prediction for hemisphere heating distribution.

Buck, G. M.↗

NASA NTRS1990

Laser-induced fluorescence of phosphors for remote cryogenic thermometry

Beshears, D. L.↗

NASA NTRS1989

Quantitative surface temperature measurement using two-color thermographic phosphors and video equipment

A thermal imaging system provides quantitative temperature information and is particularly useful in hypersonic wind tunnel applications. An object to be measured is prepared by coating with a two-color, ultraviolet-activated, thermographic phosphor. The colors emitted by the phosphor are detected by a conventional color video camera. A phosphor emitting blue and green light with a ratio that varies depending on temperature is used so that the intensity of light in the blue and green wavelengths detected by the blue and green tubes in the video camera can be compared. Signals representing the intensity of blue and green light at points on the surface of a model in a hypersonic wind tunnel are used to calculate a ratio of blue to green light intensity which provides quantitative temperature information for the surface of the model.

Buck, Gregory M.↗

NASA NTRSDate not supplied

Temperature Sensing to Above 1500 °C Using Y 2 SiO 5 :Er Phosphor Thermometry

A transition from metallic to ceramic turbine components that can operate at higher turbine engine temperatures will push component surface temperatures from below 1200 °C into a 1300 to 1500 °C temperature range that is much more challenging for phosphor thermometry measurements. To address this challenge, Y 2 SiO 5 :Er was selected for its high temperature sensing performance by both luminescence lifetime and luminescence intensity ratio (LIR) methods as well as its thermochemical compatibility with the current generation of rare earth silicate environmental barrier coatings (EBCs) that are required to protect SiC/SiC ceramic composite components. Lifetime measurements that monitor the Er3+ 4S3/2→4I15/2 emission decay at 542 nm exhibited a slow decrease in decay time with temperature up to 1300° C, above which the decay decreased steeply to provide good temperature sensitivity in the 1300 to 1500 °C range (Fig. 1). LIR images were obtained where each pixel represented the ratio I488/I561 (I488 and I561 are the detected 488 nm 4F7/2→4I15/2 and the 561 nm 4S3/2→4I15/2 emission band intensities, respectively). Good temperature sensitivity (Fig. 2) and signal-to-background ratios were observed to above 1500 °C. Contrary to conventional guidance on selecting phosphors for high temperature sensing, the detected emission band intensities and decay times exhibited remarkably slow decreases with temperature up into the 1300 to 1500 °C range despite high phonon energies (>900 cm-1) that allow the energy gap between the 4S3/2 emitting reservoir level and the 4F9/2 level below it to be bridged by as few as three phonons. The benefits of utilizing a thermographic phosphor at very high temperatures that exhibits strong nonradiative multiphonon relaxation even at room temperature is explained by a competition between spontaneous and stimulated multiphonon emission, and the more temperature-sensitive decay time above 1300 °C is explained by a transition from high to low effective phonon energies.

temperature measurement↗

NASA NTRS2018

Temperature Mapping Above and Below Air Film-Cooled Thermal Barrier Coatings Using Phosphor Thermometry

Thermal barrier coatings (TBCs) are typically used in conjunction with air film cooling to maximize overall cooling effectiveness and reliability while minimizing sacrifices in engine performance. The effects of thermal barrier coating (TBC) thermal protection and air film cooling effectiveness have usually been studied separately; however, their contributions to combined cooling effectiveness are interdependent and are not simply additive. The combined cooling effectiveness is always less than the sum of the cooling effectiveness of stand-alone TBC protection and stand-alone air film cooling. These diminishing returns arise because adding the thermally insulating TBC between the cooling air and the surface to be cooled reduces the air film cooling effectiveness and because the air film cooling reduces the heat flux through the TBC and therefore reduces the temperature difference sustained across the TBC thickness. Due to these considerations, combined cooling effectiveness must be measured to achieve an optimum balance between TBC thermal protection and air film cooling. In this investigation, temperature mapping above and below air film-cooled TBCs was performed using luminescence lifetime imaging-based phosphor thermometry. Measurements were performed in the NASA GRC Mach 0.3 burner rig on a TBC-coated plate using a scaled-up cooling hole geometry where both the hot mainstream gas temperature and the blowing ratio were varied. Surface temperature maps were obtained from a Cr-doped GdAlO3 thermographic phosphor deposited on the surface of the electron-beam vapor-deposited yttria-stabilized zirconia (YSZ) TBC. From separate plates, temperature maps from the bottom of the TBC were obtained from a thin Er-doped YSZ layer integrated into the TBC below the overlying undoped YSZ. Procedures for temperature and cooling effectiveness mapping above and below the air film-cooled TBC surface are described. Most importantly, these measurements enable mapping the combined cooling effectiveness below the TBC, which is more important than surface cooling effectiveness when there is a barrier coating between the hot mainstream gas and the surface that needs thermal protection. Advantages of the luminescence lifetime imaging method over infrared thermography, as well as its limitations to steady-state conditions are discussed.

cooling effectiveness.↗

NASA NTRS1979

Technology development for phosphoric acid fuel cell powerplant (phase 2)

The status of technology for the manufacturing and testing of 1200 sq. cm cell materials, components, and stacks for on-site integrated energy systems is assessed. Topics covered include: (1) preparation of thin layers of silicon carbide; (2) definition and control schemes for volume changes in phosphoric acid fuel cells; (3) preparation of low resin content graphite phenolic resin composites; (4) chemical corrosion of graphite-phenolic resin composites in hot phosphoric acid; (5) analysis of electrical resistance of composite materials for fuel cells; and (6) fuel cell performance and testing.

Christner, L.↗

NASA NTRS1981

Images of single X-ray photons from X-ray phosphor screens

Photographs show the efficiency and resolution characteristics of single X-ray photons converted to optical photons in a variety of commercial X-ray phosphor screens. The recording system uses a cooled, two-stage image intensifier system with fiber optics coupling to the phosphor screen. High efficiencies in the energy range 20-100 keV with position resolution of the order 200 microns are readily achievable, although the sensitive area is presently limited. Potential applications include X-ray astronomy, high-speed X-ray diffractometry, and extremely low dose radiography.

Fishman, G. J.↗

NASA NTRS1982

Stabilizing platinum in phosphoric acid fuel cells

Platinum sintering on phosphoric acid fuel cell cathodes is discussed. The cathode of the phosphoric acid fuel cell uses a high surface area platinum catalyst dispersed on a conductive carbon support to minimize both cathode polarization and fabrication costs. During operation, however, the active surface area of these electrodes decreases, which in turn leads to decreased cell performance. This loss of active surface area is a major factor in the degradation of fuel cell performance over time.

Remick, R. J.↗

NASA NTRS1984

Preparation and evaluation of advanced catalysts for phosphoric acid fuel cells

The platinum electrocatalysts were characterized for their crystallite sizes and the degree of dispersion on the carbon supports. One application of these electrocatalysts was for anodic oxidation of hydrogen in hot phosphoric acid fuel cells, coupled with the influence of low concentrations of carbon monoxide in the fuel gas stream. In a similar way, these platinum on carbon electrocatalysts were evaluated for oxygen reduction in hot phosphoric acid. Binary noble metal alloys were prepared for anodic oxidation of hydrogen and noble metal-refractory metal mixtures were prepared for oxygen reduction. An exemplar alloy of platinum and palladium (50/50 atom %) was discovered for anodic oxidation of hydrogen in the presence of carbon monoxide, and patent disclosures were submitted. For the cathode, platinum-vanadium alloys were prepared showing improved performance over pure platinum. Preliminary experiments on electrocatalyst utilization in electrode structures showed low utilization of the noble metal when the electrocatalyst loading exceeded one weight percent on the carbon.

Stonehart, P.↗

NASA NTRS1987

Organometallic catalysts for primary phosphoric acid fuel cells

A continuing effort by the U.S. Department of Energy to improve the competitiveness of the phosphoric acid fuel cell by improving cell performance and/or reducing cell cost is discussed. Cathode improvement, both in performance and cost, available through the use of a class of organometallic cathode catalysts, the tetraazaannulenes (TAAs), was investigated. A new mixed catalyst was identified which provides improved cathode performance without the need for the use of a noble metal. This mixed catalyst was tested under load for 1000 hr. in full cell at 160 to 200 C in phosphoric acid H3PO4, and was shown to provide stable performance. The mixed catalyst contains an organometallic to catalyze electroreduction of oxygen to hydrogen peroxide and a metal to catalyze further electroreduction of the hydrogen peroxide to water. Cathodes containing an exemplar mixed catalyst (e.g., Co bisphenyl TAA/Mn) operate at approximately 650 mV vs DHE in 160 C, 85% H3PO4 with oxygen as reactant. In developing this mixed catalyst, a broad spectrum of TAAs were prepared, tested in half-cell and in a rotating ring-disk electrode system. TAAs found to facilitate the production of hydrogen peroxide in electroreduction were shown to be preferred TAAs for use in the mixed catalyst. Manganese (Mn) was identified as a preferred metal because it is capable of catalyzing hydrogen peroxide electroreduction, is lower in cost and is of less strategic importance than platinum, the cathode catalyst normally used in the fuel cell.

Walsh, Fraser↗

NASA NTRS1986

Materials characterization of phosphoric acid fuel cell system

The component materials used in the fabrication of phosphoric acid fuel cells (PAFC) must have mechanical, chemical, and electrochemical stability to withstand the moderately high temperature (200 C) and pressure (500 kPa) and highly oxidizing nature of phosphoric acid. This study discusses the chemical and structural stability, performance and corrosion data on certain catalysts, catalyst supports, and electrode support materials used in PAFC applications.

Venkatesh, Srinivasan↗

NASA NTRS1992

Phosphor Scanner For Imaging X-Ray Diffraction

Improved optoelectronic scanning apparatus generates digitized image of x-ray image recorded in phosphor. Scanning fiber-optic probe supplies laser light stimulating luminescence in areas of phosphor exposed to x rays. Luminescence passes through probe and fiber to integrating sphere and photomultiplier. Sensitivity and resolution exceed previously available scanners. Intended for use in x-ray crystallography, medical radiography, and molecular biology.

Carter, Daniel C.↗

NASA NTRS1990

An intensified CCD detector using the phosphor TPB

The Research Amplifying Imaging Detector consists of a microchannel plate image intensifier with a thin coating (3500-10,000 A) of the phosphor tetraphenyl-butadiene (TPB) on the entrance window to convert EUV radiation to visible, and coupled via a lens to a CCD detector. This design allows great flexibility in selecting the pixel size and field of view, with a simple mechanical design. The phosphor appears to be quite rugged, with no degradation having appeared during several months of testing both in and out of vacuum. Tests have been made at visible and EUV (304 A) wavelengths of the following performance aspects: EUV spectral sensitivity, spatial resolution (both of components and of the system as a whole), noise, linearity, and dynamic range. An improved detector for the Coronal Diagnostic Spectrometer experiment on the Solar Heliospheric Observatory satellite is being presently designed.

Thompson, William T.↗

NASA NTRS1991

Measurements of the effects of thermal contact resistance on steady state heat transfer in phosphoric-acid fuel cell stack

The influence of the thermal contact resistance on the heat transfer between the electrode plates, and the cooling system plate in a phosphoric-acid fuel-cell stack was experimentally investigated. The investigation was conducted using a set-up that simulates the operating conditions prevailing in a phosphoric acid fuel-cell stack. The fuel-cell cooling system utilized three types of coolants, water, engine oil, and air, to remove excess heat generated in the cell electrode and to maintain a reasonably uniform temperature distribution in the electrode plate. The thermal contact resistance was measured as a function of pressure at the interface between the electrode plate and the cooling system plate. The interface pressure range was from 0 kPa to 3448 kPa, while the Reynolds number for the cooling limits varied from 15 to 79 for oil, 1165 to 6165 for water, and 700 to 6864 for air. Results showed that increasing the interface pressure resulted in a higher heat transfer coefficient.

Abdul-Aziz, Ali↗