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High Temperature Protonic Conductors

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

Dynys, Fred↗

Fuel-Cell Electrolytes Based on Organosilica Hybrid Proton Conductors

A new membrane composite material that combines an organosilica proton conductor with perfluorinated Nafion material to achieve good proton conductivity and high-temperature performance for membranes used for fuel cells in stationary, transportation, and portable applications has been developed. To achieve high proton conductivities of the order of 10(exp -1)S/cm over a wide range of temperatures, a composite membrane based on a new class of mesoporous, proton-conducting, hydrogen-bonded organosilica, used with Nafion, will allow for water retention and high proton conductivity over a wider range of temperatures than currently offered by Nafion alone. At the time of this reporting, this innovation is at the concept level. Some of the materials and processes investigated have shown good proton conductivity, but membranes have not yet been prepared and demonstrated.

Narayan, Sri R.↗

Nuclear Microprobe using Elastic Recoil Detection (ERD) for Hydrogen Profiling in High Temperature Protonic Conductors

The interaction between hydrogen and various high temperature protonic conductors (HTPC) has not been clearly understood due to poor densification and unreacted secondary phases. the melt-processing technique is used in producing fully dense simple SrCe(0.9)Y (0.10) O(3-delta) and complex Sr3Ca(1+x)Nb(2+x)O(9-delta) perovskites that can not be achieved by solid-state sintering. the possibilities of ion beam analysis have been investigated to quantify hydrogen distribution in HTPC perovskites subjected to water heat treatment. Nuclear microprobe technique is based on the interactions of a focused ion beam of MeV light ions (H-1, H-2, He-3, He-4,.) with the sample to be analyzed to determine local elemental concentrations at the cubic micrometer scale, the elastic recoil detection analysis technique (ERDA) has been carried out using He-4(+) microbeams and detecting the resulting recoil protons. Mappings of longitudinal sections of water treated SrCeO3 and Sr(Ca(1/3)Nb(2/3))O3 perovskites have been achieved, the water treatment strongly alters the surface of simple SrCe(0.9)Y(0.10)O(3-delta) perovskite. From Rutherford Back Scattering measurements (RBS), both Ce depletion and surface re-deposition is evidenced. the ERDA investigations on water treated Sr3Ca(1+x)Nb(2+x)O(9-delta) perovskite did not exhibit any spatial difference for the hydrogen incorporation from the surface to the centre. the amount of hydrogen incorporation for Sr3Ca(1+x)Nb(2+x)O(9-delta) was low and required further development of two less conventional techniques, ERDA in forward geometry and forward elastic diffusion H-1(p,p) H-1 with coincidence detection.

Berger, Pascal↗

High-Temperature Proton-Conducting Ceramics Developed

High-temperature protonic conductors (HTPC) are needed for hydrogen separation, hydrogen sensors, fuel cells, and hydrogen production from fossil fuels. The HTPC materials for hydrogen separation at high temperatures are foreseen to be metal oxides with the perovskite structure A(sup 2+)B(sup 4+)C(sup 2-, sub 3) and with the trivalent cation (M(sup 3+)) substitution at the B(sup 4+)-site to introduce oxygen vacancies. The high affinity for hydrogen ions (H(sup +)) is advantageous for protonic transport, but it increases the reactivity toward water (H2O) and carbon dioxide (CO2), which can lead to premature membrane failure. In addition, there are considerable technological challenges related to the processing of HTPC materials. The high melting point and multi-cation chemistry of HTPC materials creates difficulties in in achieving high-density, single-phase membranes by solid-state sintering. The presence of secondary phases and grain-boundary interfaces are detrimental to the protonic conduction and environmental stability of polycrystalline HTPC materials.

Sayir, Ali↗

Advances in solid polymer electrolyte fuel cell technology with low-platinum-loading electrodes

The Gemini Space program demonstrated the first major application of fuel cell systems. Solid polymer electrolyte fuel cells were used as auxiliary power sources in the spacecraft. There has been considerable progress in this technology since then, particularly with the substitution of Nafion for the polystyrene sulfonate membrane as the electrolyte. Until recently the performance was good only with high platinum loading (4 mg/sq cm) electrodes. Methods are presented to advance the technology by (1) use of low platinum loading (0.35 mg/sq cm) electrodes; (2) optimization of anode/membrane/cathode interfaces by hot pressing; (3) pressurization of reactant gases, which is most important when air is used as cathodic reactant; and (4) adequate humidification of reactant gases to overcome the water management problem. The high performance of the fuel cell with the low loading of platinum appears to be due to the extension of the three dimensional reaction zone by introduction of a proton conductor, Nafion. This was confirmed by cyclic voltammetry.

Srinivasan, Supramaniam↗

High energy efficiency and high power density proton exchange membrane fuel cells: Electrode kinetics and mass transport

The development of proton exchange membrane (PEM) fuel cell power plants with high energy efficiencies and high power densities is gaining momentum because of the vital need of such high levels of performance for extraterrestrial (space, underwater) and terrestrial (power source for electric vehicles) applications. Since 1987, considerable progress has been made in achieving energy efficiencies of about 60 percent at a current density of 200 mA/sq cm and high power densities (greater than 1 W/sq cm) in PEM fuel cells with high (4 mg/sq cm) or low (0.4 mg/sq cm) platinum loadings in electrodes. The following areas are discussed: (1) methods to obtain these high levels of performance with low Pt loading electrodes - by proton conductor impregnation into electrodes, localization of Pt near front surface; (2) a novel microelectrode technique which yields electrode kinetic parameters for oxygen reduction and mass transport parameters; (3) demonstration of lack of water transport from anode to cathode; (4) modeling analysis of PEM fuel cell for comparison with experimental results and predicting further improvements in performance; and (5) recommendations of needed research and development for achieving the above goals.

Supramaniam Srinivasan↗

NASA Tech Briefs, May 2008

Topics covered inclde: Deployable Wireless Camera Penetrators; Hand-Held Units for Short-Range Wireless Biotelemetry; Wearable Wireless Telemetry System for Implantable BioMEMS Sensors; Electronic Escape Trails for Firefighters; Architecture for a High-to-Medium-Voltage Power Converter; 24-Way Radial Power Combiner/Divider for 31 to 36 GHz; Three-Stage InP Submillimeter-Wave MMIC Amplifier; Fast Electromechanical Switches Based on Carbon Nanotubes; Solid-State High-Temperature Power Cells; Fast Offset Laser Phase-Locking System; Fabricating High-Resolution X-Ray Collimators; Embossed Teflon AF Laminate Membrane Microfluidic Diaphragm Valves; Flipperons for Improved Aerodynamic Performance; System Estimates Radius of Curvature of a Segmented Mirror; Refractory Ceramic Foams for Novel Applications; Self-Deploying Trusses Containing Shape-Memory Polymers; Fuel-Cell Electrolytes Based on Organosilica Hybrid Proton Conductors; Molecules for Fluorescence Detection of Specific Chemicals; Cell-Detection Technique for Automated Patch Clamping; Redesigned Human Metabolic Simulator; Compact, Highly Stable Ion Atomic Clock; LiGa(OTf)(sub 4) as an Electrolyte Salt for Li-Ion Cells; Compact Dielectric-Rod White-Light Delay Lines; Single-Mode WGM Resonators Fabricated by Diamond Turning; Mitigating Photon Jitter in Optical PPM Communication; MACOS Version 3.31; Fiber-Optic Determination of N2, O2, and Fuel Vapor in the Ullage of Liquid-Fuel Tanks; Spiking Neurons for Analysis of Patterns; Symmetric Phase-Only Filtering in Particle-Image Velocimetry; Efficient Coupler for a Bessel Beam Dispersive Element; and Attitude and Translation Control of a Solar Sail Vehicle.

Source record↗

Plasma Deflection Test Setup for E-Sail Propulsion Concept

The Electronic Sail or E-Sail is a novel propulsion concept based on momentum exchange between fast solar wind protons and the plasma sheath of long positively charged conductors comprising the E-Sail. The effective sail area increases with decreasing plasma density allowing an E-Sail craft to continue to accelerate at predicted ranges well beyond the capabilities of existing electronic or chemical propulsion spacecraft. While negatively charged conductors in plasmas have been extensively studied and flown, the interaction between plasma and a positively charged conductor is not well studied. We present a plasma deflection test method using a differential ion flux probe (DIFP). The DIFP measures the angle and energy of incident ions. The plasma sheath around a charged body can measured by comparing the angular distribution of ions with and without a positively charged test body. These test results will be used to evaluate numerical calculations of expected thrust per unit length of conductor in the solar wind plasma. This work was supported by a NASA Space Technology Research Fellowship.

Andersen, Allen↗

Thermal management of advanced fuel cell power systems

It is shown that fuel cell devices are particularly attractive for the high-efficiency, high-reliability space hardware necessary to support upcoming space missions. These low-temperature hydrogen-oxygen systems necessarily operate with two-phase water. In either PEMFCs (proton exchange membrane fuel cells) or AFCs (alkaline fuel cells), engineering design must be critically focused on both stack temperature control and on the relative humidity control necessary to sustain appropriate conductivity within the ionic conductor. Water must also be removed promptly from the hardware. Present designs for AFC space hardware accomplish thermal management through two coupled cooling loops, both driven by a heat transfer fluid, and involve a recirculation fan to remove water and heat from the stack. There appears to be a certain advantage in using product water for these purposes within PEM hardware, because in that case a single fluid can serve both to control stack temperature, operating simultaneously as a heat transfer medium and through evaporation, and to provide the gas-phase moisture levels necessary to set the ionic conductor at appropriate performance levels. Moreover, the humidification cooling process automatically follows current loads. This design may remove the necessity for recirculation gas fans, thus demonstrating the long-term reliability essential for future space power hardware.

Vanderborgh, N. E.↗

Charged-particle absorption by Io

The electrostatic field associated with the rotation of Jupiter, relative to the rest frame of Io, would be distorted if the satellite were an electrical conductor. An idealized two-dimensional model of the distorted electric-field configuration, in the limit of a perfectly conducting satellite or satellite ionosphere, has been constructed and used to trace the adiabatic guiding-center trajectories of energetic protons and electrons across Jupiter's magnetic field lines, which are taken as rectilinear. The adiabatic trajectories of very low-energy particles (cold plasma) are found to avoid the satellite and escape absorption. In the limit of very high particle energies, the adiabatic trajectories are undistorted, and absorption proceeds as if Io were an insulator. The interpolation between these limits is monotonic for protons, such that Io sweeps out a drift shell half as wide as the satellite for first invariants of the order of 1 GeV per gauss. The situation for electrons is more complicated, and no absorption from adiabatic trajectories is found at first invariants not exceeding 46 GeV per gauss. Electrons having first invariants of at least 50 GeV per gauss are typically swept out of drift shells wider than the satellite itself. However, electrons can impact only a portion of Io's exposed hemisphere for first invariants of 50-200 GeV per gauss. Thus, the particle-absorbing characteristics of an electrically conducting Jovian satellite are found to depend on both the species and the energy of the incident particle, and the satellite's particle-absorbing cross section differs systematically from its geometric cross section.

Schulz, M.↗

Improved Anode for a Direct Methanol Fuel Cell

A modified chemical composition has been devised to improve the performance of the anode of a direct methanol fuel cell. The main feature of the modified composition is the incorporation of hydrous ruthenium oxide into the anode structure. This modification can reduce the internal electrical resistance of the cell and increase the degree of utilization of the anode catalyst. As a result, a higher anode current density can be sustained with a smaller amount of anode catalyst. These improvements can translate into a smaller fuel-cell system and higher efficiency of conversion. Some background information is helpful for understanding the benefit afforded by the addition of hydrous ruthenium oxide. The anode of a direct methanol fuel cell sustains the electro-oxidation of methanol to carbon dioxide in the reaction CH3OH + H2O--->CO2 + 6H(+) + 6e(-). An electrocatalyst is needed to enable this reaction to occur. The catalyst that offers the highest activity is an alloy of approximately equal numbers of atoms of the noble metals platinum and ruthenium. The anode is made of a composite material that includes high-surface-area Pt/Ru alloy particles and a proton-conducting ionomeric material. This composite is usually deposited onto a polymer-electrolyte (proton-conducting) membrane and onto an anode gas-diffusion/current-collector sheet that is subsequently bonded to the proton-conducting membrane by hot pressing. Heretofore, the areal density of noble-metal catalyst typically needed for high performance has been about 8 mg/cm2. However, not all of the catalyst has been utilized in the catalyzed electro-oxidation reaction. Increasing the degree of utilization of the catalyst would make it possible to improve the performance of the cell for a given catalyst loading and/or reduce the catalyst loading (thereby reducing the cost of the cell). The use of carbon and possibly other electronic conductors in the catalyst layer has been proposed for increasing the utilization of the catalyst by increasing electrical connectivity between catalyst particles. However, the relatively low density of carbon results in thick catalyst layers that impede the mass transport of methanol to the catalytic sites. Also, the electrical conductivity of carbon is less than 1/300th of typical metals. Furthermore, the polymer-electrolyte membrane material is acidic and most metals are not chemically stable in contact with it. Finally, a material that conducts electrons (but not protons) does not contribute to the needed transport of protons produced in the electro-oxidation reaction.

Valdez, Thomas↗

High temperature (Al2O3) insulation and light weight conductors

The of an aluminum conductor with an aluminum oxide insulation film was investigated. Aluminum oxide insulated wire or strip (with a melting point of 2050 C) is unique for applications in the electronic, missile, atomic reactor, aerospace, and aircraft industries. The oxide film is highly flexible, suitable for all windings of any size and shape of coil (magnetic). Briefly touched upon are the ultraviolet, proton gamma radiation uses, as well as high vacuum and cryogenic applications. Since the film is inorganic and chemically inert, it does not age or deteriorate in storage and has good dielectric properties (1000 volts per mil).

Walker, H.↗

Solar Power System Evaluated for the Human Exploration of Mars

The electric power system is a crucial element of any mission for the human exploration of the Martian surface. The bulk of the power generated will be delivered to crew life support systems, extravehicular activity suits, robotic vehicles, and predeployed in situ resource utilization (ISRU) equipment. In one mission scenario, before the crew departs for Mars, the ISRU plant operates for 435 days producing liquefied methane and oxygen for ascent-stage propellants and water for crew life support. About 200 days after ISRU production is completed, the crew arrives for a 500-day surface stay. In this scenario, the power system must operate for a total of 1130 days (equivalent to 1100 Martian "sols"), providing 400 MW-hr of energy to the ISRU plant and up to 18 kW of daytime user power. A photovoltaic power-generation system with regenerative fuel cell (RFC) energy storage has been under study at the NASA Glenn Research Center at Lewis Field. The conceptual power system is dominated by the 4000- m2 class photovoltaic array that is deployed orthogonally as four tent structures, each approximately 5 m on a side and 100-m long. The structures are composed of composite members deployed by an articulating mast, an inflatable boom, or rover vehicles, and are subsequently anchored to the ground. Array panels consist of thin polymer membranes with thin-film solar cells. The array is divided into eight independent electrical sections with solar cell strings operating at 600 V. Energy storage is provided by regenerative fuel cells based on hydrogen-oxygen proton exchange membrane technology. Hydrogen and oxygen reactants are stored in gaseous form at 3000 psi, and the water produced is stored at 14.7 psi. The fuel cell operating temperature is maintained by a 40-m2 deployable pumped-fluid loop radiator that uses water as the working fluid. The power management and distribution (PMAD) architecture features eight independent, regulated 600-Vdc channels. Power management and distribution power cables use various gauges of copper conductors with ethylene tetrafluoroethylene insulation. To assess power system design options and sizing, we developed a dedicated Fortran code to predict detailed power system performance and estimate system mass. This code also modeled the requisite Mars surface environments: solar insolation, Sun angles, dust storms, dust deposition, and thermal and ultraviolet radiation. Using this code, trade studies were performed to assess performance and mass sensitivities to power system design parameters (photovoltaic array geometry and orientation) and mission parameters (landing date and landing site latitude, terrain slope, and dust storm activity). Mission analysis cases were also run. Power results are shown in this graph for an analysis case with a September 1, 2012, landing date; 18.95 North latitude landing site; two seasonal dusts storms; and tent arrays. To meet user load requirements and the ISRU energy requirement, an 8-metric ton (MT) power system and 4000-m2 photovoltaic array area were required for the assumed advanced CuInS2 thin-film solar cell technology. In this figure, the top curve is the average daytime photovoltaic array power, the middle curve is average daytime user load power, and the bottom curve is nighttime power. At mission day 1, daytime user power exceeds 120 kW before falling off to 80 kW at the end of the mission. Throughout the mission, nighttime user power is set to the nighttime power requirement. In this analysis, "nighttime" is defined as the 13- to 15-hr period when array power output is below the daytime power requirement. During dust storms, power system capability falls off dramatically so that by mission day 900, a daily energy balance cannot be maintained. Under these conditions, the ISRU plant is placed in standby mode, and the regenerative fuel cell energy storage is gradually discharged to meet user loads.

Kerslake, Thomas W.↗

Irradiation with molecular hydrogen as an accelerated total dose hardness assurance test method for bipolar linear circuits

High dose rate irradiation with hydrogen stress is proposed as an accelerated total dose test method for bipolar linear circuits. The method is validated across process and circuit technologies with five parts that are commonly used in space: a comparator (LM193 from National Semi-conductor), a voltage regulator (HSYE-117 RH from Intersil), a voltage reference (LT1019 from Linear Technology), a JFET input op amp (OP42 from Analog Devices) and a temperature transducer (AD590 from Analog Devices). The testing technique could rapidly establish an upper bound to the low dose rate response of parts in space and help with the part selection process in the design phase of a mission. The technology dependence and the viability of this technique are qualitatively explored using a physical model describing the dose rate response and the effect of hydrogen in bipolar technologies. The model uses four core processes: 1) space charge effects, 2) free electron/hole pair recombination, hole-hydrogen defect reactions in the oxides and 4) proton depassivation of dangling bonds at the Si/SiO2 interface. Radiation hardness assurance implications are discussed.

Pease, Ron↗

Measurement of LET distribution and dose equivalent on board the space shuttle STS-65

Space radiation dosimetry measurements have been made on board the Space Shuttle STS-65 in the Second International Microgravity Laboratory (IML-2). In these measurements, three kinds of detectors were used; one is a newly developed active detector telescope called "Real-time Radiation Monitoring Device (RRMD)" utilizing silicon semi-conductor detectors and others are conventional detectors of thermoluminescence dosimeters (TLDs) and CR-39 plastic track detectors. Using the RRMD detector, the first attempt of real-time monitoring of space radiation has been achieved successfully for a continuous period of 251.3 h, giving the temporal variations of LET distribution, particle count rates, and rates of absorbed dose and dose equivalent. The RRMD results indicate that a clear enhancement of the number of trapped particles is seen at the South Atlantic Anomaly (SAA) without clear enhancement of dose equivalent, while some daily periodic enhancements of dose equivalent due to high LET particles are seen at the lower geomagnetic cutoff regions for galactic cosmic ray particles (GCRs). Therefore, the main contribution to dose equivalent is seen to be due to GCRs in this low altitude mission (300 km). Also, the dose equivalent rates obtained by TLDs and CR-39 ranged from 146.9 to 165.2 microSv/day and the average quality factors from 1.45 to 1.57 depending on the locations and directions of detectors inside the Space-lab at this highly protected orbit for space radiation with a small inclination (28.5 degrees) and a low altitude (300 km). The LET distributions obtained by two different detectors, RRMD and CR-39, are in good agreement in the region of 15-200 keV/mm and difference of these distributions in the regions of LET < 15 keV/mm and LET > 200 keV/mm can be explained by considering characteristics of CR-39 etched track formation especially for the low LET tracks.

manned↗

Measurements of LET distribution and dose equivalent onboard the Space Shuttle IML-2 (STS-65) and S/MM#4 (STS-79)

Space radiation dosimetry measurements have been made onboard the Space Shuttle STS-65 in the Second International Microgravity Laboratory (IML-2: 28.5 degrees x 300 km: 14.68 days) and the STS-79 in the 4th Shuttle MIR mission (S/MM#4: 51.6 degrees x 300-400km: 10.2 days). In these measurements, three kinds of detectors were used; one is a newly developed active detector telescope called "Real-time Radiation Monitoring Device (RRMD-I for IML-2 and RRMD-II with improved triggering system for S/MM#4)" utilizing silicon semi-conductor detectors and the other detectors are conventional passive detectors of thermoluminescence dosimeters (TLDs) and CR-39 plastic track detectors. The main contribution to dose equivalent for particles with LET > 5.0 keV/micrometer (IML-2) and LET > 3.5 keV/micrometer (S/MM#4) is seen to be due to galactic cosmic rays (GCRs) and the contribution of the South Atlantic Anomaly (SAA) is less than 5% (IML-2: 28.5 degrees x 300 km) and 15% (S/MM#4: 51.6 degrees x 400 km) in the above RRMD LET detection conditions. For the whole LET range (> 0.2 kev/micrometer) obtained by TLDs and CR-39 in these two typical orbits (a small inclination x low altitude and a large inclination x high altitude), absorbed dose rates range from 94 to 114 microGy/day, dose equivalent rates from 186 to 207 microSv/day and average quality factors from 1.82 to 2.00 depending on the locations and directions of detectors inside the Spacelab at the highly protected IML-2 orbit (28.5 degrees x 300 km), and also, absorbed dose rates range from 290 to 367 microGy/day, dose equivalent rates from 582 to 651 microSv/day and average quality factors from 1.78 to 2.01 depending on the dosimeter packages around the RRMD-II "Detector Unit" at the S/MM#4 orbit (5l.6 degrees x 400km). In general, it is seen that absorbed doses depend on the orbit altitude (SAA trapped particles contribution dominant) and dose equivalents on the orbit inclination (GCR contribution dominant). The LET distributions obtained by two different types of active and passive detectors, RRMDs and CR-39, are in good agreement for LET of 15 - 200 kev/micrometer and difference of these distributions in the regions of LET < 15 kev/micrometer and LET > 200 kev/micrometer can be explained by considering characteristics of CR-39 etched track formation especially for the low LET tracks and chemical etching conditions.

manned↗