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At least 397 records · Page 22

An investigation of the degradation of Fluorinated Ethylene Propylene (FEP) copolymer thermal blanketing materials aboard LDEF in the laboratory

Samples of fluorinated ethylene propylene copolymer thermal blanketing material, recovered from the Long Duration Exposure Facility (LDEF), were investigated to determine the nature and the extent of degradation due to exposure to the low-Earth-orbit environment. Samples recovered from the ram-facing direction of LDEF, which received vacuum-ultraviolet (VUV) radiation and atomic-oxygen impingement, and samples from the trailing edge, which received almost exclusively VUV exposure, were investigated by scanning electron microscopy and atomic force microscopy. The most significant result of this investigation was found on samples that received only VUV exposure. These samples possessed a hard, embrittled surface layer that was absent from the atomic-oxygen exposed sample and from unexposed control samples. This surface layer is believed to be responsible for the 'synergistic' effect between VUV and atomic oxygen. Overall, the investigation revealed dramatically different morphologies for the two samples. The sample receiving both atomic-oxygen and VUV exposure was deeply eroded and had a characteristic 'rolling' surface morphology, while the sample that received only VUV exposure showed mild erosion and a surface morphology characterized by sharp high-frequency peaks. The morphologies observed in the LDEF samples, including the embrittled surface layer, were successfully duplicated in the laboratory.

Stiegman, A. E.↗

Theoretical performance of lithium and fluorine as a rocket propellant

Theoretical performance for liquid lithium and liquid fluorine as a rocket propellant was calculated with assumptions both of equilibrium and frozen composition during expansion. Parameters included were specific impulse, combustion-chamber temperature, nozzle-exit temperature, composition, mean molecular weight, characteristic velocity, coefficient of thrust, and ratio of nozzle-exit area to throat area. For chamber pressure of 300 pounds per square inch absolute and expansion to 1 atmosphere, the maximum equilibrium specific impulse calculated was 335.5 pound-seconds per pound. The effect of ionization on calculated performance was shown to be negligible by comparison of values of various parameters calculated both with and without ionized products of combustion.

FUELS -ROCKETS (INCLUDES FUELS AND OXIDANT)↗

Theoretical performance of liquid hydrogen and liquid fluorine as a rocket propellant

Theoretical values of performance parameters for liquid hydrogen and liquid fluorine as a rocket propellant were calculated on the assumption of equilibrium composition during the expansion process for a wide range of fuel-oxidant and expansion ratios. The parameters included were specific impulse, combustion-chamber temperature, nozzle-exit temperature, equilibrium composition, mean molecular weight, characteristic velocity, coefficient of thrust, ration of nozzle-exit area to throat area, specific heat at constant pressure, coefficient of viscosity, and coefficient of thermal conductivity. The maximum value of specific impulse was 364.6 pound-seconds per pound for a chamber pressure of 300 pounds per square inch absolute (20.41 atm) and an exit pressure of 1 atmosphere.

Gordon, Sanford↗

Theoretical performance of liquid ammonia and liquid fluorine as a rocket propellant

Theoretical values of performance parameters for liquid ammonia and liquid fluorine as a rocket propellant were calculated on the assumption of equilibrium composition during the expansion process for a wide range of fuel-oxidant and expansion ratios. The parameters included were specific impulse, combustion chamber temperature, nozzle-exit temperature, equilibrium composition, mean molecular weight, characteristic velocity, coefficient of thrust, ratio of nozzle-exit area to throat area, specific heat at constant pressure, coefficient of viscosity, and coefficient of thermal conductivity. The maximum value of specific impulse was 311.5 pound-seconds per pound for a chamber pressure of 300 pounds per square inch absolute (20.41 atm) and an exit pressure of 1 atmosphere.

COMBUSTION - ROCKET ENGINES↗

Transportation of liquid fluorine

In tests of a portable tank specially designed and constructed under Air Force Contract AF 33(616)-2229, liquid fluorine was safely transported and stored. The investigation included 82 hours of transportation in a total storage time of 2570 hours.

Ordin, Paul M↗

Fluorinated Poly(Phenylene Ether Ketones)

Fluorinated poly(phenylene ether ketones) are colorless, transparent, low-dielectric-constant, highly thermally stable polymers. Particularly suitable for use as film and coating materials in electronic and thermal-control applications such as; passivant insulating coats and interlevel dielectrics in microelectronic circuits, or as protective transparent coats on solar cells or mirrors. Solubility and transparency of 12F-PEK along with its lower dielectric constant and other properties make it more useful as dielectric film and coating material in many applications.

St. Clair, Anne K.↗

Physical and chemical properties of some new perfluoropolyalkylether lubricants prepared by direct fluorination

A series of perfluoropolyalkylether (PFPAE) fluids was synthesized by direct fluorination. Viscosity-temperature properties, oxidation stabilities, oxidation-corrosion properties, bulk modulus, lubricity, surface tension and density were measured. It was shown that as the carbon to oxygen ratio in the polymer repeating unit decreases, the viscometric properties improve, the fluids may become poorer boundary lubricants, the bulk modulus increases, the surface tension increases and the fluid density increases. The presence of difluoromethylene oxide units in the polymer does not significantly lower the oxidation and oxidation-corrosion stabilities as long as the difluoromethylene oxide units are separated by other units.

Jones, W. R., Jr.↗

Performance of Partially Fluorinated Polyimide Insulation for Aerospace Applications

Polyimide has been used extensively as the primary wiring insulation in commercial planes, military aircraft, and space vehicles due to its low weight, high service temperature, and good dielectric strength. New failure modes, however, have been associated with the use of polyimide because of the susceptibility of the insulation to pyrolization and arc tracking. A new wiring construction utilizing partially fluorinated polyimide insulation has been tested and compared with the standard military polyimide wire. Electrical properties which were investigated include AC corona inception and extinction voltages (sea level and 60,000 feet), time/current to smoke, and wire fusing time. The two constructions were also characterized in terms of their mechanical properties including abrasion resistance, dynamic cut through, and notch propagation. These test efforts and the results obtained are presented and discussed.

Hammoud, Ahmad N.↗

Increase in Levels of Stratospheric Chlorine and Fluorine Loading between 1985 and 1992

Mixing ratios of 3.44 ppbv (parts per billion by volume) and 1.23 ppbv for HCl and HF above 50 km, surrogates for total chlorine and fluorine, have been measured by the Atmospheric Trace Molecule Spectroscopy (ATMOS) experiment on a March 1992 flight of the Space Shuttle. Compared to the measured values obtained on a 1985 flight, these correspond to a 37% and 62% increase for HCl and HF, respectively. The derived trend in HCl (approx. 0.13 ppbv per year) is in good agreement with the model-predicted increase in chlorine loading of 0.13 ppbv per year, and with the measured trends in HCl total column abundance from reported ground-based observations. The main source of this change can be attributed to the release of man-made chlorofluorocarbons (CFC's) and hydro-chloro-fluoro-carbons (HCFC's). This new value for HCl represents an upper limit to the inorganic chlorine concentration in the stratosphere available for participation in photochemical processes which destroy ozone.

Gunson, M. R.↗

Temperature-Dependent Rate Constants and Substituent Effects for the Reactions of Hydroxyl Radicals With Three Partially Fluorinated Ethers

Rate constants and temperature dependencies for the reactions of OH with CF3OCH3 (HFOC-143a), CF2HOCF2H (HFOC-134), and CF3OCF2H (HFOC-125) were studied using a relative rate technique in the temperature range 298-393 K. The following absolute rate constants were derived: HFOC-143a, 1.9E-12 exp(-1555/T); HFOC-134, 1.9E-12 exp(-2006/T); HFOC-125, 4.7E-13 exp(-2095/T). Units are cm(exp 3)molecule(exp -1) s(exp -1). Substituent effects on OH abstraction rate constants are discussed, and it is shown that the CF3O group has an effect on the OH rate constants similar to that of a fluorine atom. The effects are related to changes in the C-H bond energies of the reactants (and thereby the activation energies) rather than changes in the preexponential factors. On the basis of a correlation of rate constants with bond energies, the respective D(C-H) bond strengths in the three ethers are found to be 102, 104, and 106 kcal/mol, with an uncertainty of about 1 kcal/mol.

Hsu, K.-J.↗

Intercalation of Lithium in Pitch-Based Graphitized Carbon Fibers Chemically Modified by Fluorine: Soft Carbon With or Without an Oxide Surface

The effects of carbon structure and surface oxygen on the carbon's performance as the anode in lithium-ion battery were studied. Two carbon materials were used for the electrochemical tests: soft carbon made from defluorination of graphite fluoride, and the carbon precursor from which the graphite fluoride was made. In this research the precursor was graphitized carbon fiber P-100. It was first fluorinated to form CF(0.68), then defluorinated slowly at 350 to 450 C in bromoform, and finally heated in 1000 C nitrogen before exposed to room temperature air, producing disordered soft carbon having basic surface oxides. This process caused very little carbon loss. The electrochemical test involved cycles of lithium intercalation and deintercalation using C/saturated LiI-50/50 (vol %) EC and DMC/Li half cell. The cycling test had four major results. (1) The presence of a basic oxide surface may prevent solvent from entering the carbon structure and therefore prolong the carbon's cycle life for lithium intercalation-deintercalation. (2) The disordered soft carbon can store lithium through two different mechanisms. One of them is lithium intercalation. which gives the disordered carbon an electrochemical behavior similar to its more ordered graphitic precursor. The other is unknown in its chemistry, but is responsible for the high-N,oltage portion (less than 0.3V) of the charge-discharge curve. (3) Under certain conditions, the disordered carbon can store more lithium than its precursor. (4) These sample and its precursor can intercalate at 200 mA/g. and deintercalate at a rate of 2000 mA/g without significant capacity loss.

Hung, Ching-Chen↗

Polyimides Containing Fluorine and Phosphorus for Potential Space Applications

As part of an effort to develop low color, ultraviolet (UV) radiation and atomic oxygen resistant polyimides for potential space applications, a novel diamine containing fluorine and phosphorus was synthesized and used to prepare polyimides. The approach was to combine attributes from colorless, UV resistant polyimides and atomic oxygen (AO) resistant polymers into a single material. Preparation of colorless polyimides has focused on minimization of charge transfer complex formation by incorporation of bulky substituents and disrupting conjugation by using meta-catenated monomers. AO resistant polymer technology development has focused on placing phenylphosphine oxide groups into the backbone of aromatic polymers. However, polyimides prepared utilizing this approach thus far have all exhibited significant color. Thus in an attempt to combine these features in a polyimide a new diamine, bis(3-aminophenyl)-3,5-di(trifluoromethyl)phenylphosphine oxide (TFMDA) was synthesized and used to prepare polyimides. The polyimides were cast into films and characterized for physical and mechanical properties, optical transmission and AO and UV resistance.

Connell, John W.↗

Atmospheric pressure chemical ionization of fluorinated phenols in atmospheric pressure chemical ionization mass spectrometry, tandem mass spectrometry, and ion mobility spectrometry

Atmospheric pressure chemical ionization (APCI)-mass spectrometry (MS) for fluorinated phenols (C6H5-xFxOH Where x = 0-5) in nitrogen with Cl- as the reagent ion yielded product ions of M Cl- through ion associations or (M-H)- through proton abstractions. Proton abstraction was controllable by potentials on the orifice and first lens, suggesting that some proton abstraction occurs through collision induced dissociation (CID) in the interface region. This was proven using CID of adduct ions (M Cl-) with Q2 studies where adduct ions were dissociated to Cl- or proton abstracted to (M-H)-. The extent of proton abstraction depended upon ion energy and structure in order of calculated acidities: pentafluorophenol > tetrafluorophenol > trifluorophenol > difluorophenol. Little or no proton abstraction occurred for fluorophenol, phenol, or benzyl alcohol analogs. Ion mobility spectrometry was used to determine if proton abstraction reactions passed through an adduct intermediate with thermalized ions and mobility spectra for all chemicals were obtained from 25 to 200 degrees C. Proton abstraction from M Cl- was not observed at any temperature for phenol, monofluorophenol, or difluorophenol. Mobility spectra for trifluorophenol revealed the kinetic transformations to (M-H)- either from M Cl- or from M2 Cl- directly. Proton abstraction was the predominant reaction for tetra- and penta-fluorophenols. Consequently, the evidence suggests that proton abstraction occurs from an adduct ion where the reaction barrier is reduced with increasing acidity of the O-H bond in C6H5-xFxOH.

NASA Discipline Environmental Health↗

Fluorine-Based DRIE of Fused Silica

A process of deep reactive-ion etching (DRIE) using a fluorine-based gas mixture enhanced by induction-coupled plasma (ICP) has been demonstrated to be effective in forming high-aspect-ratio three-dimensional patterns in fused silica. The patterns are defined in part by an etch mask in the form of a thick, high-quality aluminum film. The process was developed to satisfy a need to fabricate high-aspect-ratio fused-silica resonators for vibratory microgyroscopes, and could be used to satisfy similar requirements for fabricating other fused-silica components.

Yee, Karl↗

Small-Scale Mechanical Characterization of Space-Exposed Fluorinated Ethylene Propylene Recovered from the Hubble Space Telescope

Multi-layer insulation panels from the Hubble Space Telescope have been recovered after 19.1 years of on-orbit service and micro-tensile experiments have been performed to characterize the effect of space exposure on the mechanical response of the outermost layer. This outer layer, 127 m thick fluorinated ethylene propylene with a 100 nm thick vapor deposited aluminum reflective coating, maintained significant tensile ductility but exhibited a degradation of strength that scales with severity of space exposure. This change in properties is attributed to damage from incident solar flux, atomic oxygen damage, and thermal cycling.

Jones, J. S.↗

Analysis of Fluorinated Polyimides Flown on the Materials International Space Station Experiment

This Technical Memorandum documents the results from the Materials on International Space Station Experiment (MISSE) series involving fluorinated polyimide films analyzed at NASA Marshall Space Flight Center. These films may be used in thermal control, sunshield, solar sail, solar concentrator, and other lightweight polymer film applications. Results include postflight structural integrity, visual observations, determination of atomic oxygen erosion yield, and optical property changes as compared to preflight values.

Finckenor, M. M.↗

Li(+)-ligand Binding Energies and the Effect of Ligand Fluorination on the Binding Energies

The Li(+)-ligand binding energies are computed for seven ligands and their perfluoro analogs using Density Functional Theory. The bonding is mostly electrostatic in origin. Thus the size of the binding energy tends to correlate with the ligand dipole moment, however, the charge-induced dipole contribution can be sufficiently large to affect the dipole-binding energy correlation. The perfluoro species are significantly less strongly bound than their parents, because the electron withdrawing power of the fluorine reduces the ligand dipole moment.

Charles W Bauschlicher↗

On the Origin of Fluorine-Poor Apatite in Chondrite Parent Bodies

We conducted a petrologic study of apatite within one LL chondrite, six R chondrites, and six CK chondrites. These data were combined with previously published apatite data from a broader range of chondrite meteorites to determine that chondrites host either chlorapatite or hydroxylapatite with ≤33 mol% F in the apatite X-site (unless affected by partial melting by impacts, which can cause F-enrichment of residual apatite). These data indicate that either fluorapatite was not a primary condensate from the solar nebula or that it did not survive lower temperature nebular processes and/or parent body processes. Bulk-rock Cl and F data from chondrites were used to determine that the solar system has a Cl/F ratio of 10.5 ± 1.0 (3σ). The Cl/F ratios of apatite from chondrites are broadly reflective of the solar system Cl/F value, indicating that apatite in chondrites is fluorine poor because the solar system has about an order of magnitude more Cl than F. The Cl/F ratio of the solar system was combined with known apatite-melt partitioning relationships for F and Cl to predict the range of apatite compositions that would form from a melt with a chondritic Cl/F ratio. This range of apatite compositions allowed for the development of a crude model to use apatite X-site compositions from achondrites (and chondrite melt rocks) to determine whether they derive from a volatile-depleted and/or differentiated source, albeit with important caveats that are detailed in the manuscript. This study further highlights the utility of apatite as a mineralogical tool to understand the origin of volatiles (including H 2 O) and the diversity of their associated geological processes throughout the history of our solar system, including at its nascent stage.

Francis M. McCubbin↗