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At least 127 records · Page 7

Functional and Multifunctional Polymers: Materials for Smart Structures

The ultimate goal of the research in smart structures and smart materials is the development of a new generation of products/devices which will perform better than products/devices built from passive materials. There are a few examples of multilayer polymer systems which function as smart structures, e.g. a synthetic muscle which is a multilayer assembly of a poly(ethylene) layer, a gold layer, and a poly(pyrrole) layer immersed in a liquid electrolyte. Oxidation and reductions of the active pyrrole layer causes the assembly to reversibly deflect and mimic biological muscles. The drawback of such a setup is slow response times and the use of a liquid electrolyte. We have developed multifunctional polymers which will eliminate the use of a liquid electrolyte, and also because the functionalities of the polymers are within a few hundred angstroms, an improved response time to changes in the external field should be possible. Such multifunctional polymers may be classified as the futuristic 'smart materials.' These materials are composed of a number of different functionalities which work in a synergistic fashion to function as a device. The device performs on the application of an external field and such multifunctional polymers may be scientifically labeled as 'field responsive polymers.' Our group has undertaken a systematic approach to develop functional and multifunctional polymers capable of functioning as field responsive polymers. Our approach utilizes multicomponent polymer systems (block copolymers and graft copolymers), the strategy involves the preparation of block or graft copolymers where the functionalities are limited to different phases in a microphase separated system. Depending on the weight (or volume) fractions of each of the components, different microstructures are possible. And, because of the intimate contact between the functional components, an increase in the synergism between the functionalities may be observed. In this presentation, three examples of multifunctional polymers developed in our labs will be reported. The first class of multifunctional polymers are the microphase separated mixed (ionic and electronic) conducting or MIEC block copolymers. The second class being developed in our labs are the biocompatible conductive materials and the conductive fluids. The final class may be considered microwave active smart polymers.

Arnold, S.↗

Novel Applications of Magnetic Fields for Fluid Flow Control and for Simulating Variable Gravity Conditions

Static and dynamic magnetic fields have been used to control convection in many materials processing applications. In most of the applications, convection control (damping or enhancement) is achieved through the Lorentz force that can be tailored to counteract/assist dominant system flows. This technique has been successfully applied to liquids that are electrically conducting, such as high temperature melts of semiconductors, metals and alloys, etc. In liquids with low electrical conductivity such as ionic solutions of salts in water, the Lorentz force is weak and hence not very effective and alternate ways of flow control are necessary. If the salt in solution is paramagnetic then the variation of magnetic susceptibility with temperature and/or concentration can be used for flow control. For thermal buoyancy driven flows this can be accomplished in a temperature range below the Curie point of the salt. The magnetic force is proportional to the magnetic susceptibility and the product of the magnetic field and its gradient. By suitably positioning the experiment cell in the magnet, system flows can be assisted or countered, as desired. A similar approach can be extended to diamagnetic substances and fluids but the required magnetic force is considerably larger than that required for paramagnetic substances. The presentation will provide an overview of work to date on a NASA fluid physics sponsored project that aims to test the hypothesis of convective flow control using strong magnetic fields in protein crystal growth. The objective is to understand the nature of the various forces that come into play, delineate causative factors for fluid flow and to quantify them through experiments, analysis, and numerical modeling. The seminar will report specifically on the experimental results using paramagnetic salts and solutions in magnetic fields and compare them to analytical predictions. Applications of the concept to protein crystallization studies will be discussed. The use of strong magnetic fields for terrestrially simulating variable gravity environments and applications supporting the NASA Exploration Initiative will also be briefly discussed.

Ramachandran, N.↗

Rod-Coil Block Polyimide Copolymers

This invention is a series of rod-coil block polyimide copolymers that are easy to fabricate into mechanically resilient films with acceptable ionic or protonic conductivity at a variety of temperatures. The copolymers consist of short-rigid polyimide rod segments alternating with polyether coil segments. The rods and coil segments can be linear, branched or mixtures of linear and branched segments. The highly incompatible rods and coil segments phase separate, providing nanoscale channels for ion conduction. The polyimide segments provide dimensional and mechanical stability and can be functionalized in a number of ways to provide specialized functions for a given application. These rod-coil black polyimide copolymers are particularly useful in the preparation of ion conductive membranes for use in the manufacture of fuel cells and lithium based polymer batteries.

Mary Ann B Meador↗

Structural evolution, electrochemical kinetic properties, and stability of A-site doped perovskite Sr(1-x)Yb(x)CoO(3-δ)

Mixed ionic and electronic conducting (MIEC) perovskite SrCoO(3-δ) is a widely studied (electro)catalyst for the oxygen reduction reaction (ORR) and possesses different crystal structures at different temperatures. These temperature dependent phase transitions significantly impact the ordering of oxygen vacancies and electrochemical kinetic properties as well as the reliability of the related devices. Some of the crystal structures formed, e.g. hexagonal phases, turn out to be almost impermeable to oxygen gas. Therefore, it is important to stabilize the crystal structure of SrCoO(3-δ) that favors the ORR over a wide temperature range. Herein, the partial substitution of the A-site Sr with Yb is systematically studied, including synthesis, characterization and analysis of structural evolution, electrochemical kinetic properties, thermal stability, and stability in a CO2-containing atmosphere. The results indicate that Sr(0.90)Yb(0.10)CoO(3-δ) is able to stabilize the tetragonal crystal structure with less ordered oxygen vacancies, leading to polarization resistances of 0.051, 0.115 and 0.272 U sq.cm at 750, 700 and 650 °C, respectively, on symmetrical cells. Sr(0.90)Yb(0.10)CoO(3-δ) demonstrates a very stable surface oxygen vacancy distribution and electronic structure near oxygen vacancies but dissociation of adsorbed oxygen molecules into atomic oxygen is affected by surface Sr segregation, and polarization resistance degradation is mainly induced by surface Sr segregation. Furthermore, Sr(0.90)Yb(0.10)CoO(3-δ) exhibits excellent thermal stability as well as excellent recovery stability and improved polarization performance after a few pure air/CO2-containing air treatment cycles at 700 °C. However, a hysteresis behavior of polarization performance is observed at 650 °C during gas cycling treatment, which may cause long-term degradation of the Sr(0.90)Yb(0.10)CoO(3-δ) electrode. The different polarization behaviors during gas cycling treatment are induced by different sensitivities of the formed surface strontium carbonate and chemisorbed surface oxo-carbonaceous species to different operating temperatures.

electrochemical kinetic↗

Composite Electrolytes for Lithium Batteries: Ionic Liquids in APTES Crosslinked Polymers

Solvent free polymer electrolytes were made consisting of Li(+) and pyrrolidinium salts of trifluoromethanesulfonimide added to a series of hyperbranched poly(ethylene oxide)s (PEO). The polymers were connected by triazine linkages and crosslinked by a sol-gel process to provide mechanical strength. The connecting PEO groups were varied to help understand the effects of polymer structure on electrolyte conductivity in the presence of ionic liquids. Polymers were also made that contain poly(dimethylsiloxane) groups, which provide increased flexibility without interacting with lithium ions. When large amounts of ionic liquid are added, there is little dependence of conductivity on the polymer structure. However, when smaller amounts of ionic liquid are added, the inherent conductivity of the polymer becomes a factor. These electrolytes are more conductive than those made with high molecular weight PEO imbibed with ionic liquids at ambient temperatures, due to the amorphous nature of the polymer.

Tigelaar, Dean M.↗

Lithium-Based High Energy Density Flow Batteries

Systems and methods in accordance with embodiments of the invention implement a lithium-based high energy density flow battery. In one embodiment, a lithium-based high energy density flow battery includes a first anodic conductive solution that includes a lithium polyaromatic hydrocarbon complex dissolved in a solvent, a second cathodic conductive solution that includes a cathodic complex dissolved in a solvent, a solid lithium ion conductor disposed so as to separate the first solution from the second solution, such that the first conductive solution, the second conductive solution, and the solid lithium ionic conductor define a circuit, where when the circuit is closed, lithium from the lithium polyaromatic hydrocarbon complex in the first conductive solution dissociates from the lithium polyaromatic hydrocarbon complex, migrates through the solid lithium ionic conductor, and associates with the cathodic complex of the second conductive solution, and a current is generated.

Bugga, Ratnakumar V.↗

Electrostatically controlled heat shutter

A heat transfer assembly for conducting thermal energy is described. The assembly includes a hermetically sealed container enclosing a quantity of inert gas such as nitrogen. Two opposed walls of the container have high thermal conducting characteristics while the connecting walls have low thermal conducting characteristics. Electrodes are positioned adjacent to the high thermal conducing walls and biased relative to the conducting walls to a corona potential for creating an ionic gas wind which must contact the conducting walls to be neutralized. The contact of the gas molecules permits the maximum thermal energy transfer between the walls. Baffles can be positioned adjacent to the electrodes to regulate gas flow between the high thermal conducting surfaces.

Derr, L. J.↗

Design guidelines for hybrid microcircuits; organic adhesives for hybrid microcircuits

The properties of organic adhesives were studied to acquire an adequate information base to generate a guideline document for the selection of adhesives for use in high reliability hybrid microcircuits. Specific areas covered include: (1) alternate methods for determining the outgassing of cured adhesives; (2) effects of long term aging at 150C on the electrical properties of conductive adhesives; (3) effects of shelf life age on adhesive characteristics; (4) bond strengths of electrically conductive adhesives on thick film gold metallization, (5) a copper filled adhesive; (6) effects of products outgassed from cured adhesives on device electrical parameters; (7) metal migration from electrically conductive adhesives; and (8) ionic content of electrically insulative adhesives. The tests performed during these investigations are described, and the results obtained are discussed in detail.

Perkins, K. L.↗

Investigation of organic adhesives for hybrid microcircuits

The properties of organic adhesives were investigated to acquire information for a guideline document regarding the selection of adhesives for use in high reliability hybrid microcircuits. Specifically, investigations were made of (1) alternate methods for determining the outgassing of cured adhesives, (2) effects of long term aging at 150 C on the electrical properties of conductive adhesives, (3) effects of shelf life age on adhesive characteristics, (4) bond strengths of electrically conductive adhesives on thick film gold metallization, (5) a copper filled adhesive, (6) effects of products outgassed from cured adhesives on device electrical parameters, (7) metal migration from electrically conductive adhesives, and (8) ionic content of electrically insulative adhesives. The tests performed during these investigations are described, and the results obtained are discussed.

Perkins, K. L.↗

The effect of electrode temperature on the sparking voltage of short spark gaps

This report presents the results of an investigation to determine what effect the temperature of spark plug electrodes might have on the voltage at which a spark occurred. A spark gap was set up so that one electrode could be heated to temperatures up to 700 degrees C., while the other electrode and the air in the gap were maintained at room temperature. The sparking voltages were measured both with direct voltage and with voltage impulse from ignition coil. It was found that the sparking voltage of the gap decreased materially with increase of temperature. This change was more marked when the hot electrode was of negative polarity. The phenomena observed can be explained by the ionic theory of gaseous conduction, and serve to account for certain hitherto unexplained actions in the operation of internal combustion engines. These results indicate that the ignition spark will pass more readily when the spark-plug design is such as to make the electrodes run hot. This possible gain is, however, very closely limited by the danger of producing preignition. These experiments also show that sparking is somewhat easier when the hot electrode (which is almost always the central electrode) is negative than when the polarity is reversed.

Silsbee, F B↗

Spacecraft Water Impurity Monitor, a System for Water Quality Analysis on Exploration Missions Beyond Low Earth Orbit

Exploration missions beyond low-earth-orbit (LEO) will require advanced instrumentation to monitor water quality. Traveling beyond LEO means the transfer of water samples to an Earth-based laboratory for detailed analysis is not feasible. Detailed analysis of water composition during exploration is still necessary, because having the capability to determine the specific organic chemical causing a change in total organic carbon (TOC) or the specific metal or ionic species causing a change in conductivity has the potential to inform the crew health and system management decisions. On a new vehicle such as a lunar or Mars surface habitat or a Mars transit vehicle, finding “new” impurities not seen on ISS should be expected. The key is to identify the impurity so the correct action can be taken. On ISS we can measure TOC, conductivity, and other physical properties but do not have the capability for detailed analysis using vehicle instrumentation. This is acceptable because ISS can send samples down to Earth for further analysis and obtain the detailed composition. The Spacecraft Water Impurity Monitor (SWIM) will provide detailed water quality analysis for missions in which sample down mass is not available. SWIM is a system comprising organic and inorganic analysis modules. For organic chemicals, a gas chromatograph mass spectrometer (GCMS) detects and identifies organic impurities. For inorganic species, a capillary electrophoresis capacitively coupled contactless conductivity detection (CE-C4D) system as well as ion specific electrodes detect and identify metal ions and other inorganic salts / acids. The SWIM technology demonstration project has completed a System Requirements Review (SRR) to finalize detection requirements and is currently working to refine vehicle interface requirements for a future technology demonstration. The project also has begun preliminary flight design activities for the core analyzers in the instrument suite.

Water Monitoring↗

Spacecraft Water Impurity Monitor, a System for Water Quality Analysis on Exploration Missions Beyond Low Earth Orbit

Exploration missions beyond low-earth-orbit (LEO) will require advanced instrumentation to monitor water quality. Traveling beyond LEO means the transfer of water samples to an Earth-based laboratory for detailed analysis is not feasible. Detailed analysis of water composition during exploration is still necessary, because having the capability to determine the specific organic chemical causing a change in total organic carbon (TOC) or the specific metal or ionic species causing a change in conductivity has the potential to inform the crew health and system management decisions. On a new vehicle such as a lunar or Mars surface habitat or a Mars transit vehicle, finding “new” impurities not seen on ISS should be expected. The key is to identify the impurity so the correct action can be taken. On ISS we can measure TOC, conductivity, and other physical properties but do not have the capability for detailed analysis using vehicle instrumentation. This is acceptable because ISS can send samples down to Earth for further analysis and obtain the detailed composition. The Spacecraft Water Impurity Monitor (SWIM) will provide detailed water quality analysis for missions in which sample down mass is not available. SWIM is a system comprising organic and inorganic analysis modules. For organic chemicals, a gas chromatograph mass spectrometer (GCMS) detects and identifies organic impurities. For inorganic species, a capillary electrophoresis capacitively coupled contactless conductivity detection (CE-C4D) system as well as ion specific electrodes detect and identify metal ions and other inorganic salts / acids. The SWIM technology demonstration project has completed a System Requirements Review (SRR) to finalize detection requirements and is currently working to refine vehicle interface requirements for a future technology demonstration. The project also has begun preliminary flight design activities for the core analyzers in the instrument suite.

Water Monitoring↗

Alkali oxide-tantalum oxide and alkali oxide-niobium oxide ionic conductors

A search was made for new cationic conducting phases in alkali-tantalate and niobate systems. The phase equilibrium diagrams were constructed for the six binary systems Nb2O5-LiNbO3, Nb2O5-NaNbO3, Nb2O5-KNbO3, Ta2O5-NaTaO3, Ta2O5-LiTaO3, and Ta2O5-KTaO3. Various other binary and ternary systems were also examined. Pellets of nineteen phases were evaluated (by the sponsoring agency) by dielectric loss measurements. Attempts were made to grow large crystals of eight different phases. The system Ta2O5-KTaO3 contains at least three phases which showed peaks in dielectric loss vs. temperature. All three contain structures related to the tungsten bronzes with alkali ions in non-stoichiometric crystallographic positions.

Roth, R. S.↗

Ionic Liquids and New Proton Exchange Membranes for Fuel Cells

There is currently a great surge of activity in fuel cell research as laboratories across the world seek to take advantage of the high energy capacity provided by &el cells relative to those of other portable electrochemical power systems. Much of this activity is aimed at high temperature fie1 cells, and a vital component of such &el cells must be the availability of a high temperature stable proton-permeable membrane. NASA Glenn Research Center is greatly involved in developing this technology. Other approaches to the high temperature fuel cell involve the use of single- component or almost-single-component electrolytes that provide a path for protons through the cell. A heavily researched case is the phosphoric acid fuel cell, in which the electrolyte is almost pure phosphoric acid and the cathode reaction produces water directly. The phosphoric acid fie1 cell delivers an open circuit voltage of 0.9 V falling to about 0.7 V under operating conditions at 170 C. The proton transport mechanism is mainly vehicular in character according to the viscosity/conductance relation. Here we describe some Proton Transfer Ionic Liquids (PTILs) with low vapor pressure and high temperature stability that have conductivities of unprecedented magnitude for non-aqueous systems. The first requirement of an ionic liquid is that, contrary to experience with most liquids consisting of ions, it must have a melting point that is not much above room temperature. The limit commonly suggested is 100 C. PTILs constitute an interesting class of non-corrosive proton-exchange electrolyte, which can serve well in high temperature (T = 100 - 250 C) fuel cell applications. We will present cell performance data showing that the open circuit voltage output, and the performance of a simple H2(g)Pt/PTIL/Pt/O2(g) fuel cell may be superior to those of the equivalent phosphoric acid electrolyte fuel cell both at ambient temperature and temperatures up to and above 200 C. My work at NASA Glenn Research Center during this summer is to develop and characterize proton exchange membranes doped with ionic liquids. The main techniques used to characterize these materials are: Impedance Spectroscopy, NMR, DSC, TGA, DMA, IR, and SEM ...

Belieres, Jean-Philippe↗

Hybrid MD-Nernst Planck Model of Alpha-hemolysin Conductance Properties

Motivated by experiments in which an applied electric field translocates polynucleotides through an alpha-hemolysin protein channel causing ionic current transient blockade, a hybrid simulation model is proposed to predict the conductance properties of the open channel. Time scales corresponding to ion permeation processes are reached using the Poisson-Nemst-Planck (PNP) electro-diffusion model in which both solvent and local ion concentrations are represented as a continuum. The diffusion coefficients of the ions (K(+) and Cl(-)) input in the PNP model are, however, calculated from all-atom molecular dynamics (MD). In the MD simulations, a reduced representation of the channel is used. The channel is solvated in a 1 M KCI solution, and an external electric field is applied. The pore specific diffusion coefficients for both ionic species are reduced 5-7 times in comparison to bulk values. Significant statistical variations (17-45%) of the pore-ions diffusivities are observed. Within the statistics, the ionic diffusivities remain invariable for a range of external applied voltages between 30 and 240mV. In the 2D-PNP calculations, the pore stem is approximated by a smooth cylinder of radius approx. 9A with two constriction blocks where the radius is reduced to approx. 6A. The electrostatic potential includes the contribution from the atomistic charges. The MD-PNP model shows that the atomic charges are responsible for the rectifying behaviour and for the slight anion selectivity of the a-hemolysin pore. Independent of the hierarchy between the anion and cation diffusivities, the anionic contribution to the total ionic current will dominate. The predictions of the MD-PNP model are in good agreement with experimental data and give confidence in the present approach of bridging time scales by combining a microscopic and macroscopic model.

Cozmuta, Ioana↗

Conductivity of boules of single crystal sodium beta-alumina

The ionic and electrochemical polarization characteristics of two boules of single crystal sodium beta-alumina (Na2O.8Al2O3), 2 cm in diameter, were investigated over the range of 25 to 300 C using 2- and 4-probe ac and dc techniques with reversible and ion-blocking electrodes. Textural (or internal) polarization at 27 C was present only in boule 1 which cleaved easily. Interfacial polarization, using solid sodium electrodes, was present at 27 C in the 2-probe conductivities for both boules. Cleaning with liquid sodium at 300 C reduced its magnitude, but some interfacial polarization was still present in the 2-probe conductivities for boule 2 below about 140 C. Above 140 C, with liquid sodium electrodes, the 2-probe conductivities, essentially polarization-free, were given by KT = 3300 exp(-3650/RT). The conductivity of boule 2 at 180 C remained essentially constant with increasing current density up to about 140 milliamps per square centimeter.

Fielder, W. L.↗

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.↗

Organic acids and selected nitrogen species for ABLE-3

The NASA Global Tropospheric Experiment (GTE) executed airborne science missions aboard the NASA Wallops Electra (NA429) in the North American high latitude (greater than 45 deg North) atmosphere during Jul. to Aug. 1988 and Jul. to Aug. 1990. These missions were part of GTE's Atmospheric Boundary Layer Experiment (ABLE). The 1988 mission , ABLE-3A, examined the ecosystems of Alaska as a source and/or sink for important tropospheric gases and particles, and gained new information on the chemical composition of the Arctic atmosphere during the summertime. During 1990 the second high latitude mission, ABLE-3B, focused on the Hudson Bay Lowland and Labrador regions of Canada. Both of these missions provided benchmark data sets on atmosphere biosphere exchange and atmospheric chemistry over largely uninhabited regions of North America. In support of the GTE/ABLE-3A and -3B field missions, the University of New Hampshire flew instrumentation aboard the Wallops Electra research aircraft to provide measurements of the trace gases nitric (HNO3), formic (HCOOH), and acetic (CH3COOH) acid. In addition, measurements were conducted to determine the major water soluble ionic composition of the atmospheric aerosol. For ABLE-3B, groundbased measurements of the acidic trace gases were also performed from the NASA micrometerological tower situated at Schefferville, Laborador. These measurements were aimed at assessing dry deposition of acidic gases to the taiga ecosystem in the Laborador region of Canada.

Talbot, Robert W.↗