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NASA NTRS1988

Oxygen electrode bifunctional electrocatalyst NiCo2O4 spinel

A significant increase in energy density may be possible if a two-unit alkaline regenerative H2-O2 fuel cell is replaced with a single-unit system that uses passive means for H2O transfer and thermal control. For this single-unit system, new electrocatalysts for the O2 electrode will be required which are not only bifunctionally active but also chemically and electrochemically stable between the voltage range of about 0.7 and 1.5 V. NiCo2O4 spinel is reported to have certain characteristics that make it useful for a study of electrode fabrication techniques. High surface area NiCo2O4 powder was fabricated into unsupported, bifunctional, PTFE-bonded, porous gas fuel cell electrodes by commercial sources using varying PTFE contents and sintering temperatures. The object of this study is to measure the bifunctional activities of these electrodes and to observe what performance differences might result from different commercial electrode fabricators. O2 evolution and O2 reduction data were obtained at 80 C (31 percent KOH). An irreversible reaction (i.e., aging) occurred during O2 evolution at potentials greater than about 1.5 V. Anodic Tafel slopes of 0.06 and 0.12 V/decade were obtained for the aged electrodes. Within the range of 15 to 25 percent, the PTFE content was not a critical parameter for optimizing the electrode for O2 evolution activity. Sintering temperatures between 300 and 340 C may be adequate but heating at 275 C may not be sufficient to properly sinter the PTFE-NiCo2O4 mixture. Electrode disintegration was observed during O2 reduction. Transport of O2 to the NiCo2O4 surface became prohibitive at greater than about -0.02 A/sq cm. Cathodic Tafel slopes of -0.6 and -0.12 V/decade were assumed for the O2 reduction process. A PTFE content of 25 percent (or greater) appears to be preferable for sintering the PTFE-NiCo2O4 mixture.

Fielder, William L.↗

NASA NTRS1991

ESCA study of the effect of hydrocarbon contamination on poly(tetrafluoroethylene) exposed to atomic oxygen plasma

The ESCA spectra and data obtained by Morra et al. (1989) on poly(tetrafluoroethylene) (PTFE) exposed to atomic oxygen plasma are closely reexamined. It is shown that the spikes observed in Morra et al. plots of O/C or F/C versus time of the exposure of PTFE to atomic oxygen plasma were not characteristic of PTFE per se but were instead a result of a contamination by hydrocarbon present in their PTFE samples. This was demonstrated experimentally by comparing data derived for a very clean PTFE sample exposed for 10, 20, and 30 min to oxygen plasma with data obtained on PTFE samples with very small amounts of hydrocarbon contamination.

Golub, Morton A.↗

NASA NTRS2000

Factors Contributing to Pilot Valve Fuel Seal Extrusion in Orbiter PRCS Thrusters

Extrusion of the polytetrafluoroethylene (PTFE) pilot seal used in the monomethylhydrazine (fuel) valve of the Orbiter Primary Reaction Control System (PRCS) thrusters has been implicated in numerous on-orbit thruster failures and on-ground valve failures. Two extrusion mechanisms have been proposed, one or both may be occurring. The first mechanism is attributed to thermal expansion mismatch between adjacent PTFE and metal parts used in the fuel valve, and is referred to as thermal extrusion. The second mechanism is attributed to nitrogen tetroxide (oxidizer) leakage from the adjacent oxidizer valve on the same thruster during ground turnaround, and is referred to as oxidizer-induced extrusion. Model calculations of PTFE pilot seal in an exact pilot valve configuration show that extrusion can be caused by differential thermal expansion, without the intervening influence of oxidizer. Experimental data on semitrapped PTFE and TFM (modified PTFE) specimens simulating a fuel pilot valve configuration show that thermal extrusion 1) is incremental and irreversible, 2) increases with the size of the thermal excursion, 3) decreases with successive thermal cycling, and 4) is accompanied by gap formation. Both PTFE and TFM exhibit a higher affinity for oxidizer than fuel. The property changes associated with oxidizer uptake may explain why oxidizer seals do not exhibit extrusion. Impression replicas of fuel pilot seals removed from the Orbiter fleet show two types of extrusion: extrusion of the entire seal (loaded extrusion), or extrusion of non-sealing surface (unloaded extrusion). Both extrusion types may arise from differences in service history, rather than in failure mechanism. The plausibility oxidizer-induced extrusion was evaluated. Preliminary calculations suggest that enough energy, heat, or gas may be liberated under certain operational scenarios to cause catastrophic extrusion. However, given the lack of supporting data, conclusions implicating oxidizer leakage as a factor in extrusion must be made with caution.

Waller, J.M.↗

DOE OSTI2025

Dielectric Engineering of ZnO@ZIF‐8 for High‐Performance Triboelectric Nanogenerators and Self‐Powered Humidity Sensors

Porous metal oxide–metal-organic framework (MO x @MOF) hybrids offer synergistic effects that enhance surface charge density, electronic structure, and textural properties, making them ideal for self-powered sensing applications. Here, uniform, and pinhole-free ternary porous ZnO–PTFE@ZIF-8 hybrid films are developed on room-temperature co-sputtered ZnO–polytetrafluoroethylene (PTFE) composite films, where ZnO serves as a self-sacrificial precursor to precisely regulate ZIF-8 (Zn-MeIm 2 ) growth through solvothermal methods. The resulting TENG achieves a high output power density of 0.67 mW cm −2 , attributed to the synergistic effects of fluorine-rich PTFE and methyl-functionalized ZIF-8, which enhance surface charge density and dielectric response. By tuning PTFE content in the ZnO–PTFE composite, the dielectric constant and triboelectric output is optimized. The ZP60@ZIF-8-based device also demonstrates excellent humidity sensing performance, with a wide detection range (20–99% RH) and ultrahigh sensitivity (R V % of 19 900%, R I % of 19 325% at 99% RH). These results position ZP@ZIF-8-based TENGs as promising platforms for next-generation self-powered sensors and smart wearable electronics.

42 ENGINEERING↗

NASA NTRS1980

Tissue response to peritoneal implants

Peritoneal implants were fabricated from poly 2-OH, ethyl methacrylate (HEMA), polyetherurethane (polytetramethylene glycol 1000 MW, 1,4 methylene disocynate, and ethyl diamine), and untreated and sputter treated polytetrafluoroethylene (PTFE). The sputter treated PTFE implants were produced by an 8 cm diameter argon ion source. The treated samples consisted of ion beam sputter polished samples, sputter etched samples (to produce a microscopic surface cone texture) and surface pitted samples (produced by ion beam sputtering to result in 50 microns wide by 100 microns deep square pits). These materials were implanted in rats for periods ranging from 30 minutes to 14 days. The results were evaluated with regard to cell type and attachment kinetics onto the different materials. Scanning electron microscopy and histological sections were also evaluated. In general the smooth hydrophobic surfaces attracted less cells than the ion etched PTFE or the HEMA samples. The ion etching was observed to enhance cell attachment, multinucleated giant cell (MNGC) formation, cell to cell contact, and fibrous capsule formation. The cell responsed in the case of ion etched PTFE to an altered surface morphology. However, equally interesting was the similar attachment kinetics of HEMA verses the ion etched PTFE. However, HEMA resulted in a markedly different response with no MNGC's formation, minimal to no capsule formation, and sample coverage by a uniform cell layer.

Picha, G. J.↗

NASA NTRS1988

Transfer Lubrication For Cryogenic Bearings

Report presents evaluation of bronze-filled polytetrafluoroethylene (PTFE), known as Salox M, as cage material for ball bearings in high-pressure turbopumps for liquid oxygen. Material evaluated as potentially longer-lived replacement for glass-filled PTFE, known as Armalon. Cage transfers PTFE to balls to form solid lubricant film. However, glass fibers in glass-filled material tend to interfere with transfer. Two cage-design concepts developed; one involves metal-reinforced cage of bronze-filled PTFE; other calls for bronze-filled PTFE inserts in metal structure.

Barber, S. A.↗

NASA NTRS1991

XPS study of the effect of hydrocarbon contamination on polytetrafluoroethylene (teflon) exposed to atomic oxygen

The presence of hydrocarbon contamination on the surface of polytetrafluoroethylene (PTFE) markedly affects the oxygen uptake, and hence the wettability, of this polymer when exposed to an oxygen plasma. As revealed by X-ray photoelectron spectroscopy (XPS) analysis, the oxygen-to-carbon ratio (O/C) for such a polymer can increase sharply, and correspondingly the fluorine-to-carbon ratio (F/C) can decrease sharply, at very short exposure times; at longer times, however, such changes in the O/C and F/C ratios reverse direction, and these ratios then assume values similar to those of the unexposed PTFE. The greater the extent of hydrocarbon contamination in the PTFE, the larger are the amplitudes of the 'spikes' in the O/C- and F/C-exposure time plots. In contrast, a pristine PTFE experiences a very small, monotonic increase of surface oxidation or O/C ratio with time of exposure to oxygen atoms, while the F/C ratio is virtually unchanged from that of the unexposed polymer (2.0). Unless the presence of adventitious hydrocarbon is taken into account, anomalous surface properties relating to polymer adhesion may be improperly ascribed to PTFE exposed to an oxygen plasma.

Golub, Morton A.↗

NASA NTRS1998

Fluoropolymer Films Deposited by Argon Ion-Beam Sputtering of Polytetrafluoroethylene

The FT-IR, XPS and UV spectra of fluoropolymer films (SPTFE-I) deposited by argon ion-beam sputtering of polytetrafluoroethylene (PTFE) were obtained and compared with prior corresponding spectra of fluoropolymer films (SPTFE-P) deposited by argon rf plasma sputtering of PTFE. Although the F/C ratios for SPTFE-I and -P (1.63 and 1.51) were similar, their structures were quite different in that there was a much higher concentration of CF2 groups in SPTFE-I than in SPTFE-P, ca. 61 and 33% of the total carbon contents, respectively. The FT-IR spectra reflect that difference, that for SPTFE-I showing a distinct doublet at 1210 and 1150 per centimeter while that for SPTFE-P presents a broad, featureless band at ca. 1250 per centimeter. The absorbance of the 1210-per centimeter band in SPTFE-I was proportional to the thickness of the film, in the range of 50-400 nanometers. The SPTFE-I was more transparent in the UV than SPTFE-P at comparable thickness. The mechanism for SPTFE-I formation likely involves "chopping off" of oligomeric segments of PTFE as an accompaniment to "plasma" polymerization of TFE monomer or other fluorocarbon fragments generated in situ from PTFE on impact with energetic Ar ions. Data are presented for SPTFE-I deposits and the associated Ar(+) bombarded PTFE targets where a fresh target was used for each run or a single target was used for a sequence of runs.

Golub, Morton A.↗

NASA NTRS1995

Association of particulate air pollution and acute mortality: involvement of ultrafine particles?

Recent epidemiological studies show an association between particulate air pollution and acute mortality and morbidity down to ambient particle concentrations below 100 micrograms/m3. Whether this association also implies a causality between acute health effects and particle exposure at these low levels is unclear at this time; no mechanism is known that would explain such dramatic effects of low ambient particle concentrations. Based on results of our past and most recent inhalation studies with ultrafine particles in rats, we propose that such particles, that is, particles below approximately 50 nm in diameter, may contribute to the observed increased mortality and morbidity In the past we demonstrated that inhalation of highly insoluble particles of low intrinsic toxicity, such as TiO2, results in significantly increased pulmonary inflammatory responses when their size is in the ultrafine particle range, approximately 20 nm in diameter. However, these effects were not of an acute nature and occurred only after prolonged inhalation exposure of the aggregated ultrafine particles at concentrations in the milligrams per cubic meter range. In contrast, in the course of our most recent studies with thermodegradation products of polytetrafluoroethylene (PTFE) we found that freshly generated PTFE fumes containing singlet ultrafine particles (median diameter 26 nm) were highly toxic to rats at inhaled concentrations of 0.7-1.0 x 10(6) particles/cm3, resulting in acute hemorrhagic pulmonary inflammation and death after 10-30 min of exposure. We also found that work performance of the rats in a running wheel was severely affected by PTFE fume exposure. These results confirm reports from other laboratories of the highly toxic nature of PTFE fumes, which cannot be attributed to gas-phase components of these fumes such as HF, carbonylfluoride, or perfluoroisobutylene, or to reactive radicals. The calculated mass concentration of the inhaled ultrafine PTFE particles in our studies was less than 60 micrograms/m3, a very low value to cause mortality in healthy rats. Aging of the fumes with concomitant aggregation of the ultrafine particles significantly decreases their toxicity. Since ultrafine particles are always present in the urban atmosphere, we suggest that they play a role in causing acute lung injury in sensitive parts of the population.

NASA Discipline Environmental Health↗

NASA NTRS2019

Impulse Measurements of Electric Solid Propellant in an Electrothermal Ablation-Fed Pulsed Plasma Thruster

Electric solid propellants are advanced solid chemical rocket propellants that can be controlled (ignited, throttled and extinguished) through the application and removal of an electric current. These propellants are also being considered for use in the ablative pulsed plasma thruster. In this paper, the performance of an electric solid propellant operating in an electrothermal ablation-fed pulsed plasma thruster was investigated using an inverted pendulum micro-Newton thrust stand. The impulse bit and specific impulse of the device using the electric solid propellant were measured for short-duration test runs of 100 pulses and longer-duration runs to end-of-life, at energy levels of 5, 10, 15 and 20 J. Also, the device was operated using the current state-of-the-art ablation-fed pulsed plasma thruster propellant, polytetrafluoroethylene or PTFE. Impulse bit measurements for PTFE indicate 100±20 μN-s at an initial energy level of 5 J, which increases linearly by ~30 μN-s/J with increased initial energy. Measurements of the impulse bit for the electric solid propellant are on average lower than PTFE by 10% or less. Specific impulse for when operating on PTFE is calculated to be about 450 s compared to 225 s for the electric solid propellant. The 50% reduction in specific impulse is due to increased mass ablated during operation with the electric solid propellant relative to PTFE.

Glascock, Matthew S.↗

NASA NTRS1972

Adhesion and transfer of polytetrafluoroethylene to tungsten studied by field ion microscopy

Mechanical contacts between polytetrafluoroethylene (PTFE) and tungsten field ion tips were made in situ in the field ion microscope. Both load and force of adhesion were measured for varying contact times and for clean and contaminated tungsten tips. Strong adhesion between the PTFE and clean tungsten was observed at contact times greater than 2.5 min (forces of adhesion were greater than three times the load). For times less than 2.5 min, the force of adhesion was immeasurably small. The increase in adhesion with contact time after 2.5 min can be attributed to the increase in true contact area by creep of PTFE. No adhesion was measurable at long contact times with contaminated tungsten tips. Neon field ion micrographs taken after the contacts show many linear and branched arrays which appear to represent PTFE that remains adhered to the surface even at the high electric fields required for imaging.

Brainard, W. A.↗

NASA NTRS1972

Adhesion and transfer of polytetrafluorethylene to metals studied by Auger emission spectroscopy

The adhesion and transfer of polytetrafluoroethylene (PTFE) to metals in ultrahigh vacuum were studied. The transfer was effected both by compressive static contact and by sliding contact. The transfer observed after static contact was independent of the chemical constitution of the substrate. Electron-induced desorption of the fluorine in the transferred PTFE showed that the fluorine had no chemical interaction with the metal substrate. The coefficient of friction on metals was independent of the chemical constitution of the substrate. However, sliding PTFE on soft metals, such as aluminum, generated wear fragments that lodged in the PTFE and machined the substrate.

Pepper, S. V.↗

NASA NTRS1973

Scanning electron microscope study of polytetrafluoroethylene sliding on aluminum single crystals

Friction experiments were conducted in air with polytetrafluoroethylene (PTFE) sliding on aluminum single crystals. Mechanical scoring of the crystals with (110) and (100) orientations was observed with a single pass of the PTFE slider. No scoring was observed on the (111). The degree of scoring of the crystals is related to the hardness, with the hardest surface (111) showing no damage and the softest surface (110) showing the most severe scoring. Scoring is caused by work-hardened pieces of aluminum which, as a consequence of the adhesion between PTFE and aluminum, were pulled out of the bulk and became embedded in the PTFE polymer.

Brainard, W. A.↗

NASA NTRS1973

The atomic nature of polymer-metal interactions in adhesion, friction and wear

Adhesion experiments with polytetra-fluoroethylene (PTFE) and polyimide contacting tungsten indicate that the polymers bond chemically to the clean metal surface. Polymer chain fragments which transfer to the surface of tungsten in field ion microscopy adhesion studies are highly oriented. Auger emission spectroscopy of PTFE transfer films to various metal surfaces indicates that the PTFE is bonded to the metal surface via the carbon atom. With PTFE in sliding contact with different orientations of aluminum, metal orientation is found to influence surfaces in sliding. The lowest friction and least amount of surface damage is detected on the highest atomic density (111) plane. The friction process itself can initiate polymer film formation from simple organic molecules.

Buckley, D. H.↗

NASA NTRS1981

Cathode catalysts for primary phosphoric acid fuel cells

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

Source record↗

NASA NTRS1983

Spherical micro-glass particle impingement studies of thermoplastic materials at normal incidence

Light optical and scanning electron microscope studies were conducted to characterize the erosion resistance of polymethyl methacrylate (PMMA), polycarbonate (PC), polytetrafluoroethylene (PTFE) and ultra-high-molecular-weight-polyethylene (UHMWPE). Erosion was caused by a jet of spherical micro-glass beads at normal impact. During the initial stages of damage, the surfaces of these materials were studied using a profilometer. Material buildup above the original surface was observed on PC and PMMA. As erosion progressed, this buildup disappeared as the pit became deeper. Little or no buildup was observed on PTFE and on UHMWPE. UHMWPE and PTFE are the most resistant materials and PMMA the least. Favorable properties for high erosion resistance seem to be high values of ultimate elongation, and strain energy and a low value of the modulus of elasticity. Erosion-rate-versus-time curves of PC and PTFE exhibit incubation, acceleration and steady state periods. A continuously increasing erosion rate period was observed however for PMMA instead of a steady state period. At early stages of damage and at low impact pressure material removal mechanisms appear to be similar to those for metallic materials.

Rao, P. V.↗

NASA NTRS1982

Use of high L.E.T. radiation to improve adhesion of metals to polytetrafluoroethylene

MgK alpha X-rays (1254 eV) and 2 keV electrons irradiate the surface of polytetrafluoro ethylene (PTFE). The damage is confined to a few tenths of a micron below the surface, and the doses exceed 10 to the eight power rad. X-ray Photoelectron Spectroscopy (XPS) of the irradiated surfaces and mass spectroscopy of the gaseous products of irradiation indicate that the damaged layer is crosslinked or branched PTFE. After either type of irradiation, the surface has enhanced affinity for metals and a lower contact angle with hexadecane. Tape pull tests show that evaporated Ni and Au films adhere better to the irradiated surface. XPS shows the Ni interacts chemically with PTFE forming NiF2 and possibly NiC. However, the gold adhesion and contact angle results indicate that the interaction is, at least in part, chemically nonspecific. Decreased contact angles on FEP Teflon crystallized against gold were attributed to either the presence of a polar oxygen layer or increased physical forces due to greater density. In the case of irradiated PTFE, no oxygen on the surface was observed. The crosslinked structure might, however, have a greater density, thus accounting for the observed increase in adhesion and wettability.

Wheeler, D. R.↗

NASA NTRS1984

Spherical microglass particle impingement studies of thermoplastic materials at normal incidence

Veerabhadra Rao, P.↗