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All sourcesNASA NTRSDOE OSTI
NASA NTRS2004

Self-Healing Behavior of Ethylene-Based Ionomers

The self-healing behavior of poly(ethylene-co-methacrylic acid) (EMAA)-based ionomers holds tremendous potential for use in a wide variety of unique applications. However, to effectively utilize this self-healing behavior and to design novel materials which possess this ability, the mechanism by which they heal must first be understood ionomers are a class of polymers that can be described as copolymers containing less than 15 mol% ionic content whereby the bulk properties are governed by ionic interactions within the polymer. These ionic groups aggregate into discrete regions known as multiplets which overlap forming clusters that act as physical cross-links profoundly influencing the bulk physical properties. These clusters possess an order-disorder transition (T(sub i)) where the clustered regions may rearrange themselves given time and stimuli. Recognizing the strong influence of these ionic regions on other well understood ionomer properties, their role in self-heating behavior will be assessed. The self-healing behavior is observed following projectile puncture. It has been suggested that during impact energy is passed to the ionomer material, heating it to the melt state. After penetration, it is proposed that the ionic regions maintain their attractions and flow together patching the hole. Thus, the importance of this ionic character and is unique interaction must be established. This will be accomplished through examination of materials with varying ionic content and through the analysis of the T(sub i). The specific ionomer systems examined include a number of ethylene-based materials. Materials of varying ionic content, including the non-ionic base copolymers, will be examined by peel tests, projectile impact and DSC analysis. The information will also be compared with some basic data on LDPE material.

Kalista, Stephen J., Jr.↗
NASA NTRS1991

Some recent studies with the solid-ionomer electrochemical capacitor

Giner, Inc. has developed a high-energy-density, all-solid-ionomer electrochemical capacitor, completely free of liquid electrolyte. The novel features of this device include 1) a three-dimensional metal oxide-particulate-ionomer composite electrode structure, and 2) a unitized repeating cell element. The composite electrode structures are bonded to opposite sides of a thin sheet of a solid proton-conducting ionomer membrane and form an integrally bonded membrane and electrode assembly (MEA). Individual MEAs can be stacked in series as bipolar elements to form a multiple cell device. The discharge characteristics and energy storage properties of these devices are described. Typical capacitance measured for a unit cell is 1 F/cm(exp 2). Life testing of a multicell capacitor on an intermittent basis has shown, that over a 10,000 hour period, the capacitance and resistance of the cell has remained invariant. There has been no maintenance required on the device since it was fabricated. Other multicell units of shorter life duration have exhibited similar reliable performance characteristics. Recent work has focused on increasing the capacitance of the unitized structure and improving the low-temperature characteristics. The approaches and experimental results will be presented. Some possible advanced NASA applications for these unique all-solid-ionomer devices will be discussed.

S Sarangapani↗
NASA NTRS1991

Some Recent Studies With the Solid-Ionomer Electrochemical Capacitor

Giner, Inc., has developed a high-energy-density, all-solid-ionomer electro-chemical capacitor, completely free of liquid electrolyte. The novel features of this device include: (1) a three-dimensional metal oxide-particulate-ionomer composite electrode structure and (2) a unitized repeating cell element. The composite electrode structures are bonded to opposite sides of a thin sheet of a solid proton-conducting ionomer membrane and form an integrally bonded membrane and electrode assembly (MEA). Individual MEAs can be stacked in series as bipolar elements to form a multiple cell device. The discharge characteristics and energy storage properties of these devices are described. Typical capacitance measured for a unit cell is 1 F/cm. Life testing of a multicell capacitor on an intermittent basis has shown that, over a 10,000-hour period, the capacitance and resistance of the cell has remained invariant. There has been no maintenance required on the device since it was fabricated. Other multicell units of shorter life duration have exhibited similar reliable performance characteristics. Recent work has focused on increasing the capacitance of the unitized structure and improving the low-temperature characteristics. The approaches and experimental results will be presented. Some possible advanced NASA applications for these unique all-solid-ionomer devices will be discussed.

Sarangapani, S.↗
NASA NTRS2003

Puncture-Healing Properties of Carbon Nanotube-Filled Ionomers

Ionomers are polymers that contain ionic groups in relatively low concentrations along the polymer backbone. These ionic groups, in the presence of oppositely charged ions, form aggregates that lead to novel physical properties of the polymer. React-A-Seal(trademark) and Surlyn(trademark) are poly(ethylene-co-methacrylic acid) (EMAA) ionomer-based materials and Nucrel(trademark) is the EMAA acid copolymer neutralized to produce Surlyn(trademark). React-A-Seal(trademark), Surlyn(trademark), and Nucrel(trademark) recover into their original shapes following a high impact puncture at velocities ranging from 300 to 1200 ft/s ('self-healing'). This self-healing process may be of great benefit in space applications where structures are exposed to matter impacts. A thermal IR camera indicated a temperature increase to 98 C for Nucrel(trademark) 925, Surlyn(trademark) 8940, React-A-Seal(trademark), and Surlyn(trademark) 8920 after initial penetration. To understand and generalize the observed phenomena, questions concerning the mechanism of the puncture resealing must be answered. One suggestion is that the elastic character of the melt created by the puncture drives the self-healing. This inference is based on the observed temperature rise of approx. 3 C above the melting temperature of the samples (approx. 95 C) during the impact. With the expectation of gaining additional insight into the self-healing phenomenon, a thermodynamic and viscoelastic investigation was conducted using primarily DSC and DMA. Surlyn(trademark) and React-A-Seal(trademark) showed the characteristic order-disorder transition at approx. 52 C that has been reported in literature. Master curves were constructed from the creep isotherms for the four EMAA samples. An aging study was performed to investigate the irreproducibility and "tailing effect" observed in the creep data. The aging study indicated that, with increased aging time and temperature, changes in the polyethylene matrix lead to complexities in morphology resulting in changes in the magnitude and shape of the creep curves.

Ward, Thomas C.↗
NASA NTRS2016

Ionomer-Membrane Water Processing Apparatus

This disclosure provides water processing apparatuses, systems, and methods for recovering water from wastewater such as urine. The water processing apparatuses, systems, and methods can utilize membrane technology for extracting purified water in a single step. A containment unit can include an ionomer membrane, such as Nafion(Registered Trademark), over a hydrophobic microporous membrane, such as polytetrafluoroethylene (PTFE). The containment unit can be filled with wastewater, and the hydrophobic microporous membrane can be impermeable to liquids and solids of the wastewater but permeable to gases and vapors of the wastewater, and the ionomer membrane can be permeable to water vapor but impermeable to one or more contaminants of the gases and vapors. The containment unit can be exposed to a dry purge gas to maintain a water vapor partial pressure differential to drive permeation of the water vapor, and the water vapor can be collected and processed into potable water.

MacCallum, Taber K.↗
NASA NTRS2016

Ionomer-Membrane Water Processing Methods

This disclosure provides water processing apparatuses, systems, and methods for recovering water from wastewater such as urine. The water processing apparatuses, systems, and methods can utilize membrane technology for extracting purified water in a single step. A containment unit can include an ionomer membrane, such as Nafion(TradeMark) over a hydrophobic microporous membrane, such as polytetrafluoroethylene (PTFE). The containment unit can be filled with wastewater, and the hydrophobic microporous membrane can be impermeable to liquids and solids of the wastewater but permeable to gases and vapors of the wastewater, and the ionomer membrane can be permeable to water vapor but impermeable to one or more contaminants of the gases and vapors. The containment unit can be exposed to a dry purge gas to maintain a water vapor partial pressure differential to drive permeation of the water vapor, and the water vapor can be collected and processed into potable water.

MacCallum, Taber K.↗
NASA NTRS2017

Ionomer-Membrane Water Processing Apparatus

This disclosure provides water processing apparatuses, systems, and methods for recovering water from wastewater such as urine. The water processing apparatuses, systems, and methods can utilize membrane technology for extracting purified water in a single step. A containment unit can include an ionomer membrane, such as Nafion.RTM., over a hydrophobic microporous membrane, such as polytetrafluoroethylene (PTFE). The containment unit can be filled with wastewater, and the hydrophobic microporous membrane can be impermeable to liquids and solids of the wastewater but permeable to gases and vapors of the wastewater, and the ionomer membrane can be permeable to water vapor but impermeable to one or more contaminants of the gases and vapors. The containment unit can be exposed to a dry purge gas to maintain a water vapor partial pressure differential to drive permeation of the water vapor, and the water vapor can be collected and processed into potable water.

MacCallum, Taber K.↗
NASA NTRS2016

Contaminant Permeation in the Ionomer-Membrane Water Processor (IWP) System

The Ionomer-membrane Water Processor (IWP) is a patented membrane-distillation based urine brine water recovery system. The unique properties of the IWP membrane pair limit contaminant permeation from the brine to the recovered water and purge gas. A paper study was conducted to predict volatile trace contaminant permeation in the IWP system. Testing of a large-scale IWP Engineering Development Unit (EDU) with urine brine pretreated with the International Space Station (ISS) pretreatment formulation was then conducted to collect air and water samples for quality analysis. Distillate water quality and purge air GC-MS results are presented and compared to predictions, along with implications for the IWP brine processing system.

Kelsey, Laura K.↗
NASA NTRS1989

Advanced double layer capacitors

There is a need for large amounts of power to be delivered rapidly in a number of airborne and space systems. Conventional, portable power sources, such as batteries, are not suited to delivering high peak power pulses. The charge stored at the electrode-electrolyte double layer is, however, much more assessible on a short time scale. Devices exploiting this concept were fabricated using carbon and metal oxides (Pinnacle Research) as the electrodes and sulfuric acid as the electrolyte. The approach reported, replaces the liquid sulfuric acid electrolyte with a solid ionomer electrolyte. The challenge is to form a solid electrode-solid ionomer electrolyte composite which has a high capacitance per geometric area. The approach to maximize contact between the electrode particles and the ionomer was to impregnate the electrode particles using a liquid ionomer solution and to bond the solvent-free structure to a solid ionomer membrane. Ruthenium dioxide is the electrode material used. Three strategies are being pursued to provide for a high area electrode-ionomer contact: mixing of the RuOx with a small volume of ionomer solution followed by filtration to remove the solvent, and impregnation of the ionomer into an already formed RuOx electrode. RuOx powder and electrodes were examined by non-electrochemical techniques. X-ray diffraction has shown that the material is almost pure RuO2. The electrode structure depends on the processing technique used to introduce the Nafion. Impregnated electrodes have Nafion concentrated near the surface. Electrodes prepared by the evaporation method show large aggregates of crystals surrounded by Nafion.

Sarangapani, S.↗
NASA NTRS1999

Electro-Active Polymer (EAP) Actuators for Planetary Applications

NASA is seeking to reduce the mass, size, consumed power, and cost of the instrumentation used in its future missions. An important element of many instruments and devices is the actuation mechanism and electroactive polymers (EAP) are offering an effective alternative to current actuators. In this study, two families of EAP materials were investigated, including bending ionomers and longitudinal electrostatically driven elastomers. These materials were demonstrated to effectively actuate manipulation devices and their performance is being enhanced in this on-going study. The recent observations are reported in this paper, include the operation of the bending-EAP at conditions that exceed the harsh environment on Mars, and identify the obstacles that its properties and characteristics are posing to using them as actuators. Analysis of the electrical characteristics of the ionomer EAP showed that it is a current driven material rather than voltage driven and the conductivity distribution on the surface of the material greatly influences the bending performance. An accurate equivalent circuit modeling of the ionomer EAP performance is essential for the design of effective drive electronics. The ionomer main limitations are the fact that it needs to be moist continuously and the process of electrolysis that takes place during activation. An effective coating technique using a sprayed polymer was developed extending its operation in air from a few minutes to about four months. The coating technique effectively forms the equivalent of a skin to protect the moisture content of the ionomer. In parallel to the development of the bending EAP, the development of computer control of actuated longitudinal EAP has been pursued. An EAP driven miniature robotic arm was constructed and it is controlled by a MATLAB code to drop and lift the arm and close and open EAP fingers of a 4-finger gripper. Keywords: Miniature Robotics, Electroactive Polymers, Electroactive Actuators, EAP Materials

Bar-Cohen, Y.↗
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 NTRS2004

Polyimide/Carbon Nanotube Composite Films for Electrostatic Charge Mitigation

Low color, space environmentally durable polymeric films with sufficient electrical conductivity to mitigate electrostatic charge build-up have been under investigation as part of a materials development activity. In the work described herein, single-walled carbon nanotubes (SWNT) solutions were dispersed in solutions of a novel ionomer in N,N-dimethylacetamide resulting in homogenous suspensions or quasi-solutions. The ionomer was used to aid in the dispersal of SWNTs in to a soluble, low color space environmentally durable polyimide. The use of the ionomer as a dispersant enabled the nanotubes to be dispersed at loading levels up to 3 weight % in a polyimide solution without visual agglomeration. The films were further characterized for their electrical and mechanical properties.

Delozier, D. M.↗
NASA NTRS1989

Advanced double layer capacitors

Work was conducted that could lead to a high energy density electrochemical capacitor, completely free of liquid electrolyte. A three-dimensional RuO sub x-ionomer composite structure has been successfully formed and appears to provide an ionomer ionic linkage throughout the composite structure. Capacitance values of approximately 0.6 F/sq cm were obtained compared with 1 F/sq cm when a liquid electrolyte is used with the same configuration.

Sarangapani, S.↗
NASA NTRS2007

Water-Free Proton-Conducting Membranes for Fuel Cells

Poly-4-vinylpyridinebisulfate (P4VPBS) is a polymeric salt that has shown promise as a water-free proton-conducting material (solid electrolyte) suitable for use in membrane/electrode assemblies in fuel cells. Heretofore, proton-conducting membranes in fuel cells have been made from perfluorinated ionomers that cannot conduct protons in the absence of water and, consequently, cannot function at temperatures >100 C. In addition, the stability of perfluorinated ionomers at temperatures >100 C is questionable. However, the performances of fuel cells of the power systems of which they are parts could be improved if operating temperatures could be raised above 140 C. What is needed to make this possible is a solid-electrolyte material, such as P4VPBS, that can be cast into membranes and that both retains proton conductivity and remains stable in the desired higher operating temperature range. A family of solid-electrolyte materials different from P4VPBS was described in Anhydrous Proton-Conducting Membranes for Fuel Cells (NPO-30493), NASA Tech Briefs, Vol. 29, No. 8 (August 2005), page 48. Those materials notably include polymeric quaternized amine salts. If molecules of such a polymeric salt could be endowed with flexible chain structures, it would be possible to overcome the deficiencies of simple organic amine salts that must melt before being able to conduct protons. However, no polymeric quaternized amine salts have yet shown to be useful in this respect. The present solid electrolyte is made by quaternizing the linear polymer poly- 4-vinylpyridine (P4VP) to obtain P4VPBS. It is important to start with P4VP having a molecular weight of 160,000 daltons because P4VPBS made from lower-molecular-weight P4VP yields brittle membranes. In an experimental synthesis, P4VP was dissolved in methanol and then reacted with an excess of sulfuric acid to precipitate P4VPBS. The precipitate was recovered, washed several times with methanol to remove traces of acid, and dried to a white granular solid. In another synthesis, nanoparticles of silica rich with surface hydroxyl groups were added to P4VP in methanol solution, which was then reacted with excess sulfuric acid to precipitate granules of a composite that most probably had the composition (P4VPBS)-SiO2-SiO(HSO4)2. The granular P4VPBS produced in the first-mentioned synthesis was dissolved in water to make a glue-like, turbid solution; the granular P4VPBS/silica composite produced in the second-mentioned synthesis was mixed with water to make a turbid, glue-like suspension. The proportions of polymer salt to water in such preparations can be varied; it was found that approximately equal parts of water and polymer salt yield a solution or suspension amenable to further processing.

Narayanan, Sekharipuram↗
NASA NTRS1993

Near-ambient solid polymer fuel cell

Fuel cells are extremely attractive for extraterrestrial and terrestrial applications because of their high energy conversion efficiency without noise or environmental pollution. Among the various fuel cell systems the advanced polymer electrolyte membrane fuel cells based on sulfonated fluoropolymers (e.g., Nafion) are particularly attractive because they are fairly rugged, solid state, quite conductive, of good chemical and thermal stability and show good oxygen reduction kinetics due to the low specific adsorption of the electrolyte on the platinum catalyst. The objective of this program is to develop a solid polymer fuel cell which can efficiently operate at near ambient temperatures without ancillary components for humidification and/or pressurization of the fuel or oxidant gases. During the Phase 1 effort we fabricated novel integral electrode-membrane structures where the dispersed platinum catalyst is precipitated within the Nafion ionomer. This resulted in electrode-membrane units without interfacial barriers permitting unhindered water diffusion from cathode to anode. The integral electrode-membrane structures were tested as fuel cells operating on H2 and O2 or air at 1 to 2 atm and 10 to 50 C without gas humidification. We demonstrated that cells with completely dry membranes could be self started at room temperature and subsequently operated on dry gas for extended time. Typical room temperature low pressure operation with unoptimized electrodes yielded 100 mA/cm(exp 2) at 0.5V and maximum currents over 300 mA/cm(exp 2) with low platinum loadings. Our results clearly demonstrate that operation of proton exchange membrane fuel cells at ambient conditions is feasible. Optimization of the electrode-membrane structure is necessary to assess the full performance potential but we expect significant gains in weight and volume power density for the system. The reduced complexity will make fuel cells also attractive for smaller and portable power supplies and as replacement for batteries.

Holleck, G. L.↗
NASA NTRS1996

Development of Electrochemical Supercapacitors for EMA Applications

A limitation of the typical electrochemical capacitor is the maximum available power and energy density, and an improvement in capacitance per unit weight and volume is needed. A solid-ionomer electrochemical capacitor having a unit cell capacitance greater than 2 F/sq cm and a repeating element thickness of 6 mils has been developed. This capacitor could provide high-current pulses for electromechanical actuation (EMA). Primary project objectives were to develop high-capacitance particulates, to increase capacitor gravimetric and volumetric energy densities above baseline and to fabricate a 10-V capacitor with a repeating element thickness of 6 mils or less. Specific EMA applications were identified and capacitor weight and volume projections made.

Kosek, John A.↗
NASA NTRS2000

Thin Film Catalyst Layers for Direct Methanol Fuel Cells

One of the primary obstacles to the widespread use of the direct methanol fuel cell (DMFC) is the high cost of the catalyst. Therefore, reducing the catalyst loading well below the current level of 8-12 mg/cm 2 would be important to commercialization. The current methods for preparation of catalyst layers consisting of catalyst, ionomer and sometimes a hydrophobic additive are applied by either painting, spraying, decal transfer or screen printing processes. Sputter deposition is a coating technique widely used in manufacturing and therefore particularly attractive. In this study we have begun to explore sputtering as a method for catalyst deposition. Present experiments focus on Pt-Ru catalyst layers for the anode.

Witham, C. K.↗