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NASA NTRS1995

Performance and optimization of a combustion interface for isotope ratio monitoring gas chromatography/mass spectrometry

Conditions and systems for on-line combustion of effluents from capillary gas chromatographic columns and for removal of water vapor from product streams were tested. Organic carbon in gas chromatographic peaks 15 s wide and containing up to 30 nanomoles of carbon was quantitatively converted to CO2 by tubular combustion reactors, 200 x 0.5 mm, packed with CuO or NiO. No auxiliary source of O2 was required because oxygen was supplied by metal oxides. Spontaneous degradation of CuO limited the life of CuO reactors at T > 850 degrees C. Since NiO does not spontaneously degrade, its use might be favored, but Ni-bound carbon phases form and lead to inaccurate isotopic results at T < 1050 degrees C if gas-phase O2 is not added. For all compounds tested except CH4, equivalent isotopic results are provided by CuO at 850 degrees C, NiO + O2 (gas-phase mole fraction, 10(-3)) at 1050 degrees C and NiO at 1150 degrees C. The combustion interface did not contribute additional analytical uncertainty, thus observed standard deviations of 13C/12C ratios were within a factor of 2 of shot-noise limits. For combustion and isotopic analyses of CH4, in which quantitative combustion required T approximately 950 degrees C, NiO-based systems are preferred, and precision is approximately 2 times lower than that observed for other analytes. Water must be removed from the gas stream transmitted to the mass spectrometer or else protonation of CO2 will lead to inaccuracy in isotopic analyses. Although thresholds for this effect vary between mass spectrometers, differential permeation of H2O through Nafion tubing was effective in both cases tested, but the required length of the Nafion membrane was 4 times greater for the more sensitive mass spectrometer.

NASA Discipline Exobiology↗

NASA NTRS2004

New High-Temperature Membranes Developed for Proton Exchange Membrane Fuel Cells

Fuel cells are receiving a considerable amount of attention for potential use in a variety of areas, including the automotive industry, commercial power generation, and personal electronics. Research at the NASA Glenn Research Center has focused on the development of fuel cells for use in aerospace power systems for aircraft, unmanned air vehicles, and space transportation systems. These applications require fuel cells with higher power densities and better durability than what is required for nonaerospace uses. In addition, membrane cost is a concern for any fuel cell application. The most widely used membrane materials for proton exchange membrane (PEM) fuel cells are based on sulfonated perfluorinated polyethers, typically Nafion 117, Flemion, or Aciplex. However, these polymers are costly and do not function well at temperatures above 80 C. At higher temperatures, conventional membrane materials dry out and lose their ability to conduct protons, essential for the operation of the fuel cell. Increasing the operating temperature of PEM fuel cells from 80 to 120 C would significantly increase their power densities and enhance their durability by reducing the susceptibility of the electrode catalysts to carbon monoxide poisoning. Glenn's Polymers Branch has focused on developing new, low-cost membranes that can operate at these higher temperatures. A new series of organically modified siloxane (ORMOSIL) polymers were synthesized for use as membrane materials in a high-temperature PEM fuel cell. These polymers have an organic portion that can allow protons to transport through the polymer film and a cross-linked silica network that gives the polymers dimensional stability. These flexible xerogel polymer films are thermally stable, with decomposition onset as high as 380 C. Two types of proton-conducting ORMOSIL films have been produced: (1) NASA-A, which can coordinate many highly acid inorganic salts that facilitate proton conduction and (2) NASA-B, which has been produced and which incorporates strongly acidic (proton donating) functional groups into the polymer backbone. Both of these polymer films have demonstrated significantly higher proton conductivity than Nafion at elevated temperatures and low relative humidities. An added advantage is that these polymers are very inexpensive to produce because their starting materials are commodity chemicals that are commercially available in large volumes.

Kinder, James D.↗

NASA NTRS2016

Design, Development, and Testing of a Water Vapor Exchanger for Spacecraft Life Support Systems

Thermal and environmental control systems for future exploration spacecraft must meet challenging requirements for efficient operation and conservation of resources. Maximizing the use of regenerative systems and conserving water are critical considerations. This paper describes the design, development, and testing of an innovative water vapor exchanger (WVX) that can minimize the amount of water absorbed in, and vented from, regenerative CO2 removal systems. Key design requirements for the WVX are high air flow capacity (suitable for a crew of six), very high water recovery, and very low pressure losses. We developed fabrication and assembly methods that enable high-efficiency mass transfer in a uniform and stable array of Nafion tubes. We also developed analysis and design methods to compute mass transfer and pressure losses. We built and tested subscale units sized for flow rates of 2 and 5 cu ft/min (3.4–8.5 cu m/hr). Durability testing demonstrated that a stable core geometry was sustained over many humid/dry cycles. Pressure losses were very low (less than 0.5 in. H2O (125 Pa) total) and met requirements at prototypical flow rates. We measured water recovery efficiency across a range of flow rates and humidity levels that simulate the range of possible cabin conditions. We measured water recovery efficiencies in the range of 80 to 90%, with the best efficiency at lower flow rates and higher cabin humidity levels. We compared performance of the WVX with similar units built using an unstructured Nafion tube bundle. The WVX achieves higher water recovery efficiency with nearly an order of magnitude lower pressure drop than unstructured tube bundles. These results show that the WVX provides uniform flow through flow channels for both the humid and dry streams and can meet requirements for service on future exploration spacecraft. The WVX technology will be best suited for long-duration exploration vehicles that require regenerative CO2 removal systems while needing to conserve water.

Izenson, Michael G.↗

NASA NTRS1981

Production of hydrogen by electron transfer catalysis using conventional and photochemical means

Alternate methods of generating hydrogen from the sulfuric acid thermal or electrochemical cycles are presented. A number of processes requiring chemical, electrochemical or photochemical methods are also presented. These include the design of potential photoelectrodes and photocatalytic membranes using Ru impregnated nafion tubing, and the design of experiments to study the catalyzed electrolytic formation of hydrogen and sulfuric acid from sulfur dioxide and water using quinones as catalysts. Experiments are carried out to determine the value of these approaches to energy conversion.

Rillema, D. P.↗

NASA NTRS1986

Theoretical and Experimental Flow Cell Studies of a Hydrogen-Bromine Fuel Cell, Part 1

There is increasing interest in hydrogen-bromine fuel cells as both primary and regenerative energy storage systems. One promising design for a hydrogen-bromine fuel cell is a negative half cell having only a gas phase, which is separated by a cationic exchange membrane from a positive half cell having an aqueous electrolyte. The hydrogen gas and the aqueous bromide solution are stored external to the cell. In order to calculate the energy storage capacity and to predict and assess the performance of a single cell, the open circuit potential (OCV) must be estimated for different states of change, under various conditions. Theoretical expressions were derived to estimate the OCV of a hydrogen-bromine fuel cell. In these expressions temperature, hydrogen pressure, and bromine and hydrobromic acid concentrations were taken into consideration. Also included are the effects of the Nafion membrance separator and the various bromide complex species. Activity coefficients were taken into account in one of the expressions. The sensitivity of these parameters on the calculated OCV was studied.

Savinell, R. F.↗

NASA NTRS1985

A general, cryogenically-based analytical technique for the determination of trace quantities of volatile organic compounds in the atmosphere

An analytical technique for the determination of trace (sub-ppbv) quantities of volatile organic compounds in air was developed. A liquid nitrogen-cooled trap operated at reduced pressures in series with a Dupont Nafion-based drying tube and a gas chromatograph was utilized. The technique is capable of analyzing a variety of organic compounds, from simple alkanes to alcohols, while offering a high level of precision, peak sharpness, and sensitivity.

Coleman, R. A.↗

NASA NTRS1992

Temperature dependence of the electrode kinetics of oxygen reduction at the platinum/Nafion interface - A microelectrode investigation

Results of a study of the temperature dependence of the oxygen reduction kinetics at the Pt/Nafion interface are presented. This study was carried out in the temperature range of 30-80 C and at 5 atm of oxygen pressure. The results showed a linear increase of the Tafel slope with temperature in the low current density region, but the Tafel slope was found to be independent of temperature in the high current density region. The values of the activation energy for oxygen reduction at the platinum/Nafion interface are nearly the same as those obtained at the platinum/trifluoromethane sulfonic acid interface but less than values obtained at the Pt/H3PO4 and Pt/HClO4 interfaces. The diffusion coefficient of oxygen in Nafion increases with temperature while its solubility decreases with temperature. These temperatures also depend on the water content of the membrane.

Parthasarathy, Arvind↗

NASA NTRS1992

Pressure dependence of the oxygen reduction reaction at the platinum microelectrode/nafion interface - Electrode kinetics and mass transport

The investigation of oxygen reduction kinetics at the platinum/Nafion interface is of great importance in the advancement of proton-exchange-membrane (PEM) fuel-cell technology. This study focuses on the dependence of the oxygen reduction kinetics on oxygen pressure. Conventional Tafel analysis of the data shows that the reaction order with respect to oxygen is unity at both high and low current densities. Chronoamperometric measurements of the transport parameters for oxygen in Nafion show that oxygen dissolution follows Henry's isotherm. The diffusion coefficient of oxygen is invariant with pressure; however, the diffusion coefficient for oxygen is lower when air is used as the equilibrating gas as compared to when oxygen is used for equilibration. These results are of value in understanding the influence of O2 partial pressure on the performance of PEM fuel cells and also in elucidating the mechanism of oxygen reduction at the platinum/Nafion interface.

Parthasarathy, Arvind↗

NASA NTRS1992

Regenerative fuel cells

A development status evaluation is presented for moderate-temperature, single-unit, regenerative fuel cells using either alkaline or solid polymer proton-exchange membrane (PEM) electrolytes. Attention is given to the results thus far obtained for Pt, Ir, Rh, and Na(x)Pt3O4 catalysts. Alkaline electrolyte tests have been performed on a half-cell basis with a floating-electrode cell; PEM testing has been with complete fuel cells, using Nafion 117.

Swette, Larry L.↗

NASA NTRS1993

PEM regenerative fuel cells

This paper will update the progress in developing electrocatalyst systems and electrode structures primarily for the positive electrode of single-unit solid polymer proton exchange membrane (PEM) regenerative fuel cells. The work was done with DuPont Nafion 117 in complete fuel cells (40 sq cm electrodes). The cells were operated alternately in fuel cell mode and electrolysis mode at 80 C. In fuel cell mode, humidified hydrogen and oxygen were supplied at 207 kPa (30 psi); in electrolysis mode, water was pumped over the positive electrode and the gases were evolved at ambient pressure. Cycling data will be presented for Pt-Ir catalysts and limited bifunctional data will be presented for Pt, Ir, Ru, Rh, and Na(x)Pt3O4 catalysts as well as for electrode structure variations.

Swette, Larry L.↗

NASA NTRS1993

High power density proton exchange membrane fuel cells

Proton exchange membrane (PEM) fuel cells use a perfluorosulfonic acid solid polymer film as an electrolyte which simplifies water and electrolyte management. Their thin electrolyte layers give efficient systems of low weight, and their materials of construction show extremely long laboratory lifetimes. Their high reliability and their suitability for use in a microgravity environment makes them particularly attractive as a substitute for batteries in satellites utilizing high-power, high energy-density electrochemical energy storage systems. In this investigation, the Dow experimental PEM (XUS-13204.10) and unsupported high platinum loading electrodes yielded very high power densities, of the order of 2.5 W cm(exp -2). A platinum black loading of 5 mg per cm(exp 2) was found to be optimum. On extending the three-dimensional reaction zone of fuel cell electrodes by impregnating solid polymer electrolyte into the electrode structures, Nafion was found to give better performance than the Dow experimental PEM. The depth of penetration of the solid polymer electrolyte into electrode structures was 50-70 percent of the thickness of the platinum-catalyzed active layer. However, the degree of platinum utilization was only 16.6 percent and the roughness factor of a typical electrode was 274.

Murphy, Oliver J.↗

NASA NTRS1993

The electrolyte challenge for a direct methanol-air polymer electrolyte fuel cell operating at temperatures up to 200 C

Novel polymer electrolytes are being evaluated for use in a direct methanol-air fuel cell operating at temperatures in excess of 100 C. The evaluation includes tests of thermal stability, ionic conductivity, and vapor transport characteristics. The preliminary results obtained to date indicate that a high temperature polymer electrolyte fuel cell is feasible. For example, Nafion 117 when equilibrated with phosphoric acid has a conductivity of at least 0.4 Omega(exp -1)cm(exp -1) at temperatures up to 200 C in the presence of 400 torr of water vapor and methanol vapor cross over equivalent to 1 mA/cm(exp 2) under a one atmosphere methanol pressure differential at 135 C. Novel polymers are also showing similar encouraging results. The flexibility to modify and optimize the properties by custom synthesis of these novel polymers presents an exciting opportunity to develop an efficient and compact methanol fuel cell.

Savinell, Robert↗

NASA NTRS1995

Development of electrochemical super capacitors for EMA applications

In a NASA SBIR Phase I program (Contract No. NAS8-40119), Giner, Inc. evaluated the feasibility of fabricating an all-solid-ionomer multicell electrochemical capacitor having a unit cell capacitance greater than 2 F/sq cm and a repeating element thickness of 6 mils. This capacitor can possibly be used by NASA as a high-rate energy source for electromechanical actuator (EMA) activation for advanced space missions. The high unit cell capacitance and low repeating element thickness will allow for the fabrication of a low-volume, low-weight device, favorable characteristics for space applications. These same characteristics also make the capacitor attractive for terrestrial applications, such as load-leveling batteries or fuel cells in electric vehicle applications. Although the projected energy densities for electrochemical capacitors are about two orders of magnitude lower than that of batteries, the high-power-density characteristics of these devices render them as potentially viable candidates for meeting pulse or peak electrical power requirements for some anticipated aerospace mission scenarios, especially those with discharge times on the millisecond to second time scale. On a volumetric or gravimetric basis, the advantages of utilizing electrochemical capacitors rather than batteries for meeting the peak power demands associated with a specific mission scenario will largely depend upon the total and pulse durations of the power peaks. The effect of preparation conditions on RuO(x), the active component in an all-solid-ionomer electrochemical capacitor, was evaluated during this program. Methods were identified to prepare RuO(x) having a surface areagreater than 180 sq m/g, and a capacitance of greater than 2 F/sq cm. Further efforts to reproducibly obtain these high-surface-area materials in scaled-up batches will be evaluated in Phase 2. During this Phase 1 program we identified a superior Nafion 105 membrane, having a film thickness of 5 mils, that showed excellent performance in our all-solid-ionomer capacitors and resulted in electrochemical capacitors with a repeating element thickness of 8 mils. We are currently working with membrane manufacturers to obtain a high performance membrane in less than 3 mil thickness to obtain a repeating element thickness of 6 mils or less. A 10-cell all-solid ionomer capacitor stack, with each cell having a 222 sq cm active area, was fabricated and evaluated as part of the Phase 1 program. Further Scale-up of a high-energy-density stack is plannedin Phase 2.

Kosek, J. A.↗

NASA NTRS1995

Sensing strategies for toxic vapor detection

This work was motivated by the recommendations of the American Conference of Governmental Industrial Hygienists (ACGIH) that threshold limits for hydrazine, H2N-NH2 in air be lowered from 100 to 10 parts-per-billion (ppb) concentration levels. Hydrazine is one of the high-energy propellants used in large volumes in Space Shuttle, Titan, payloads, and other aerospace operations. Since analytical methods presently available for hydrazine detection and/or determination do not satisfy such low levels of detection, the ultimate goal of this research is the development and characterization of a portable and compact chemical sensor ideally capable to detect (in real time) 1 ppb of hydrazine, continuously and reversibly. The laboratory prototype developed as part of this project is comprised of: (1) a reactor part in which H2N-NH2 reacts, generating chemiluminescence emission, with tris(2,2'-bipyridine)ruthenium(III), which is immobilized on an ion-exchange polymeric materials of a perfluorinated hydrocarbon containing sulfonate groups as exchange centers (Nafion); (2) an electrochemical three-electrode cell posed at a potential at which the immobilized ruthenium complex could be reoxidized to the 3-oxidation state (as to provide reversible and continuous detection); and (3) a low power consumption photomultiplier tube to collect and quantitatively integrate the emitted photons with the help of auxiliary electronics and readout device.

Mottola, Horacio A.↗

NASA NTRS1996

Low Crossover Polymer Electrolyte Membranes for Direct Methanol Fuel Cells

Direct Methanol Fuel Cells (DMFC's) using polymer electrolyte membranes are promising power sources for portable and vehicular applications. State of the art technology using Nafion(R) 117 membranes (Dupont) are limited by high methanol permeability and cost, resulting in reduced fuel cell efficiencies and impractical commercialization. Therefore, much research in the fuel cell field is focused on the preparation and testing of low crossover and cost efficient polymer electrolyte membranes. The University of Southern California in cooperation with the Jet Propulsion Laboratory is focused on development of such materials. Interpenetrating polymer networks are an effective method used to blend polymer systems without forming chemical links. They provide the ability to modify physical and chemical properties of polymers by optimizing blend compositions. We have developed a novel interpenetrating polymer network based on poly (vinyl - difluoride)/cross-linked polystyrenesulfonic acid polymer composites (PVDF PSSA). Sulfonation of polystyrene accounts for protonic conductivity while the non-polar, PVDF backbone provides structural integrity in addition to methanol rejection. Precursor materials were prepared and analyzed to characterize membrane crystallinity, stability and degree of interpenetration. USC JPL PVDF-PSSA membranes were also characterized to determine methanol permeability, protonic conductivity and sulfur distribution. Membranes were fabricated into membrane electrode assemblies (MEA) and tested for single cell performance. Tests include cell performance over a wide range of temperatures (20 C - 90 C) and cathode conditions (ambient Air/O2). Methanol crossover values are measured in situ using an in-line CO2 analyzer.

Prakash, G. K. Surya↗

NASA NTRS1999

Electrical Impedance of Ionic Polymeric Metal Composites

In recent years the use of ionic polymer metal composites such as Nafion-based platinum ionomers have emerged as electroactive polymer materials with great potential for robotics and other applications. An effective activation of these materials requires understanding of their mechanism of operation. Generally, the material needs to be maintained hydrated to assure its electromechanical activity. To allow the control of the response of the material, a study is underway to investigate the electrical response. Particular emphasis is placed on possible electrochemical reactions and deviations from linear dielectric behavior. Currently, efforts are made to determine the necessary drive characteristics of the source to allow low power operation (< or = 1.0 W) of the material as an actuator.

Leary, S.↗

NASA NTRS2005

Development of a Low-Power CO2 Removal and Compression System for Closed-Loop Air Revitalization in Future Spacecraft

The current CO2 removal technology of NASA is very energy intensive and contains many non-optimized subsystems. This paper discusses the design and prototype development of a two-stage CO2 removal and compression system that will utilize much less power than NASA s current CO2 removal technology. This integrated system contains a Nafion membrane followed by a residual water adsorber that performs the function of the desiccant beds in the four-bed molecular sieve (4BMS) system of the International Space Station (ISS). The membrane and the water adsorber are followed by a two-stage CO2 removal and compression subsystem that satisfies the operations of the CO2 adsorbent beds of the 4BMS aid the interface compressor for the Sabatier reactor connection. The two-stage compressor will utilize the principles of temperature-swing adsorption (TSA) compression technology for CO2 removal and compression. The similarities in operation and cycle times of the CO2 removal (first stage) and compression (second stage) operations will allow thermal coupling of the processes to maximize the efficiency of the system. In addition to the low-power advantage, this processor will maintain a lower CO2 concentration in the cabin than that can be achieved by the existing CO2 removal systems. The compact, consolidated, configuration of membrane gas dryer and CO2 separator and compressor will allow continuous recycling of humid air in the cabin and supply of compressed CO2 to the reduction unit for oxygen recovery. The device has potential application to the International Space Station and future, long duration, transit, and planetary missions.

Mulloth, Lila M.↗

NASA NTRS1996

Modeling and Simulation of the Direct Methanol Fuel Cell

From intro.: The direct methanol liquid feed fuel cell uses aqueous solutions of methanol as fuel and oxygen or air as the oxidant and uses an ionically conducting polymer membrane such as Nafion(sup r)117 and the electrolyte. This type of direct oxidation cell is fuel versatile and offers significant advantages in terms of simplicity of design and operation...The present study focuses on the results of a phenomenological model based on current understanding of the various processed operating in these cells.

fuel cell methanol fuel cell methanol↗