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NASA NTRS1974

Hydrogen and fluorine in the surfaces of lunar samples

The resonant nuclear reaction F-19 (p, alpha gamma)0-16 has been used to perform depth sensitive analyses for both fluorine and hydrogen in lunar samples. The resonance at 0.83 MeV (center-of-mass) in this reaction has been applied to the measurement of the distribution of trapped solar protons in lunar samples to depths of about 1/2 micrometer. These results are interpreted in terms of terrestrial H2O surface contamination and a redistribution of the implanted solar H which has been influenced by heavy radiation damage in the surface region. Results are also presented for an experiment to test the penetration of H2O into laboratory glass samples which have been irradiated with 0-16 to simulate the radiation damaged surfaces of lunar glasses. Fluorine determinations have been performed in a 1 pm surface layer on lunar samples using the same F-19 alpha gamma)0-16 resonance. The data are discussed from the standpoint of lunar fluorine and Teflon contamination.

Leich, D. A.↗

NASA NTRS1975

Fluorine photochemistry in the stratosphere

The photochemistry of fluorine in the stratosphere is surveyed in order to estimate the effect on ozone of fluorine atoms released by the breakdown of chlorofluoromethanes. The catalytic efficiency for ozone destruction by fluorine is found to be less than .0001 that of chlorine in the altitude range from 25 to 50 km.

Stolarski, R. S.↗

NASA NTRS1978

Thermal analysis of a high energy propulsion system /hydrazine and liquid fluorine/ for a rover class Mars Orbiter

Maintaining cryogenic fluorine at a -189 C during the interplanetary cruise period to Mars is a major thermal problem. At this low temperature the heat rejection by radiation is severely limited and the allowable thermal load to the fluorine tank is less than approximately 8 watts. Previous studies generally constrain the spacecraft to an inline tank configuration which tends to maximize the fluorine tank's view and heat rejection to space. With the Inertial Upper Stage, sufficient stack height may not be available on the Shuttle for an inline tank configuration. Therefore, this study addresses the more thermally constraining side by side tank configuration.

Stultz, J. W.↗

NASA NTRS1979

Experience with fluorine and its safe use as a propellant

The industrial and the propulsion experience with fluorine and its derivatives is surveyed. The hazardous qualities of fluorine and safe handling procedures for the substance are emphasized. Procedures which fulfill the safety requirements during ground operations for handling fluorinated propulsion systems are discussed. Procedures to be implemented for use onboard the Space Transportation System are included.

Bond, D. L.↗

NASA NTRS1980

The hollow-cathode helium-fluorine laser

It is possible to obtain uniform stable long-pulse excitation (in excess of 100 microsec) in gas mixtures involving highly electronegative constituents (SF6, CCl4, NF3, and I2). Such a system was used to investigate the atomic fluorine laser. In the hollow cathode, lasing on fluorine transitions in the doublet system lasted for up to 80 microsec with no signs of the self-termination as reported previously in positive-column devices. The excitation process of the laser appears to depend heavily upon the fluorine donor utilized. For instance, a single-step process is involved when NF3 is used whereas a two-step process is evident for SF6. The details are discussed.

Crane, J. K.↗

NASA NTRS1988

Two-photon-excited fluorescence spectroscopy of atomic fluorine at 170 nm

Two-photon-excited fluorescence spectroscopy of atomic fluorine is reported. A doubled dye laser at 286-nm is Raman shifted in H2 to 170 nm (sixth anti-Stokes order) to excite ground-state 2P(0)J fluorine atoms to the 2D(0)J level. The fluorine atoms are detected by one of two methods: observing the fluorescence decay to the 2PJ level or observing F(+) production through the absorption of an additional photon by the excited atoms. Relative two-photon absorption cross sections to and the radiative lifetimes of the 2D(0)J states are measured.

Herring, G. C.↗

NASA NTRS1991

Two-dimensional model calculation of fluorine-containing reservoir species in the stratosphere

Two-dimensional model calculations have been carried out of the distributions of the fluorine-containing reservoir species HF, CF2O, and CFClO. HF constitutes the largest fluorine reservoir in the stratosphere, but CF2O also makes an important contribution to the inorganic fluorine budget. CFClO amounts are most important in the tropical lower stratosphere. HF amounts increase with altitude throughout the stratosphere, while those of CF2O and CFClO fall off above their mixing ratio peaks due to photolysis. The model is in good qualitative agreement with observed vertical profiles of HF and CF2O but tends to underestimate the total column of HF. The calculated CFClO distribution is in good agreement with the very limited data. The disagreement in the HF columns is likely due to small inaccuracies in the model's treatment of lower stratospheric photolysis of chlorofluorocarbons. The model results support the suggestion that CF2O may be heterogeneously converted to HF on the surface of polar stratospheric cloud particles. The model results also suggest that the quantum yield for photolysis of CF2O is near unity.

Kaye, Jack A.↗

NASA NTRS1991

The influences of fluorine and process variations on polysilicon film stress and MOSFET hot carrier effects

The use of fluorinated gate oxides may provide an improvement in nMOSFET reliability by enhancing hot carrier resistance. In order to clarify the mechanisms by which polysilicon processing and fluorination influence the oxide behavior, a matrix of nMOSFET structures was prepared using various processing, doping, and implantation strategies. These structures were evaluated for crystalline morphology and chemical element distribution. Mechanical stress measurements were taken on the polysilicon films from room temperature to cryogenic temperature. These examinations showed that fluorination of a structure with randomly oriented polysilicon can reduce residual mechanical stress and improve hot carrier resistance at room temperature.

Lowry, Lynn E.↗

NASA NTRS1992

Lunar mining of oxygen using fluorine

An important aspect of lunar mining will be the extraction of volatiles, particularly oxygen, from lunar rocks. Thermodynamic data show that oxygen could readily be recovered by fluorination of abundant lunar anorthite, CaAl2Si2O8. Fluorine is the most reactive element, and the only reagent able to extract 100 percent of the oxygen from any mineral, yet it can safely be stored or reacted in nickel or iron containers. The general fluorination reaction, mineral + 2F2 = mixed fluorides = O2, has been used for more than 30 years at a laboratory scale by stable-isotope geochemists. For anorthite, metallic Al and Si may be recovered from the mixed fluorides by Na-reduction, and CaO via exchange with Na2O; the resulting NaF may be recycled into F2 and Na by electrolysis, using lanthanide-doped CaF2 as the inert anode.

Burt, Donald M.↗

NASA NTRS1954

Preliminary Investigation of Performance and Starting Characteristics of Liquid Fluorine : Liquid Oxygen Mixtures with Jet Fuel

The performance of jet fuel with an oxidant mixture containing 70 percent liquid fluorine and 30 percent liquid oxygen by weight was investigated in a 500-pound-thrust engine operating at a chamber pressure of 300 pounds per square inch absolute. A one-oxidant-on-one-fuel skewed-hole impinging-jet injector was evaluated in a chamber of characteristic length equal to 50 inches. A maximum experimental specific impulse of 268 pound-seconds per pound was obtained at 25 percent fuel, which corresponds to 96 percent of the maximum theoretical specific impulse based on frozen composition expansion. The maximum characteristic velocity obtained was 6050 feet per second at 23 percent fuel, or 94 percent of the theoretical maximum. The average thrust coefficient was 1.38 for the 500-pound thrust combustion-chamber nozzle used, which was 99 percent of the theoretical (frozen) maximum. Mixtures of fluorine and oxygen were found to be self-igniting with jet fuel with fluorine concentrations as low as 4 percent, when low starting propellant flow rated were used.

ENGINES, ROCKET↗

NASA NTRS1958

Theoretical Rocket Performance of JP-4 Fuel with Several Fluorine-Oxygen Mixtures Assuming Equilibrium Composition

Theoretical rocket performance for equilibrium composition during expansion was calculated for JP-4 fuel with several fluorine-oxygen mixtures for a range of pressure ratios and oxidant-fuel ratios. The parameters included are specific impulse, combustion-chamber temperature, nozzle-exit temperature, molecular weight, characteristic velocity, coefficient of thrust, ratio of nozzle-exit area to throat area, specific heat at constant pressure, isentropic exponent, viscosity, thermal conductivity, and equilibrium gas compositions. A correlation is given for the effect of chamber pressure on several of the parameters. The maximum value of specific impulse for a chamber pressure of 600 pounds per square inch absolute (40.827 atm) and an exit pressure of 1 atmosphere is 325.7 for 70.37 percent fluorine in the oxidant as compared with 284.9 and 305.1 for 100 percent oxygen and 100 percent fluorine, respectively.

Gordon, Sanford↗

NASA NTRS1995

The surface properties of fluorinated polyimides exposed to VUV and atomic oxygen

The effect of atomic oxygen flux and VUV radiation alone and in combination on the surface of fluorinated polyimide films was studied using XPS spectroscopy. Exposure of fluorinated polyimides to VUV radiation alone caused no observable damage to the polymer surface, while an atomic oxygen flux resulted in substantial oxidation of the surface. On the other hand, exposure to VUV radiation and atomic oxygen in combination caused extensive oxidation of the polymer surface after only 2 minutes of exposure. The amount of oxidized carbon on the polymer surface indicated that there is aromatic ring opening oxidation. The changes in the O1s/C1s, N1s/C1s, and F1s/C1s ratios suggested that an ablative degradation process is highly favorable. A synergistic effect of VUV radiation in the presence of atomic oxygen is clearly evidenced from the XPS study. The atomic oxygen could be considered as the main factor in the degradation process of fluorinated polyimide films exposed to a low earth orbit environment.

Forsythe, John S.↗

NASA NTRS1994

Increase of carbonyl fluoride (COF2) in the stratosphere and its contribution to the 1992 budget of inorganic fluorine in the upper stratosphere

Volume mixing ratio profiles of COF2 have been derived through most of the stratosphere between 30 deg N and 54 deg S from series of 0.01-/cm resolution infrared solar spectra recorded in the occultation mode by the atmospheric trace molecule spectroscopy (ATMOS) instrument during the ATLAS 1 space shuttle mission of March-April 1992. When compared with similar results obtained from the ATMOS/Spacelab 3 mission of April-May 1985, the cumulative increase in the burden of COF2 in the middle and upper stratosphere was found to be 67% for that 7-year time interval. By combining a subset of these COF2 results with upper stratospheric concentrations of HF also derived from the ATMOS observations, it was further found that the budget of inorganic fluorine above 35 km altitude increased by (60 +/- 10)% over the 1985-1992 time interval, which corresponds to an average exponential rate of increase of (6.7 +/- 1/1)%/yr, or a linear rate of increase reference to 1985 of (8.5 +/- 1.3)%/yr at the 1 sigma confidence level. The total inorganic F atom volume mixing ratio found in the upper stratosphere for 1985 and 1992 and the increase during this perid mirror the rise in man-made fluorine-bearing compounds at the ground during the early to mid 1980s. This demonstrates the negligible impact of natural sources of fluorine, in particular volcanic activity, on the observed change in F in the upper stratosphere. Implications of the present findings and comparison with model results are discussed.

Zander, R.↗

NASA NTRS1994

Increase of carbonyl fluoride (COF2) in the stratosphere and its contribution to the 1992 budget of inorganic fluorine in the upper stratosphere

Volume mixing ratio profiles of COF2 have been derived through most of the stratosphere between 30 deg N and 54 deg S from series of 0.01-cm(exp -1) resolution infrared solar spectra recorded in the occultation mode by the atmospheric trace molecule spectroscopy (ATMOS) instrument during the ATLAS 1 space shuttle mission of March-April 1992. When compared with similar results obtained from the ATMOS/Spacelab 3 mission of April-May 1985, the cumulative increase in the burden of COF2 in the middle and upper stratosphere was found to be 67% for that 7-year time interval. By combining a subset of these COF2 results with upper stratospheric concentrations of HF also derived from the ATMOS observations, it was further found that the budget of inorganic fluorine above 35 km altitude increased by (60 +/- 10) % over the 1985-1992 time interval, which corresponds to an average exponential rate of increase of(6.7 +/- 1.1) % /yr , or a linear rate of increase referenced to 1985 of (8.5 +/- 1.3) % /yr at the 1(sigma) confidence level. The total inorganic F atom volume mixing ratio found in the upper stratosphere for 1985 and 1992 and the increase during this period mirror the rise in man-made fluorine-bearing compounds at the ground during the early to mid 1980s. This demonstrates the negligible impact of natural sources of fluorine, in particular volcanic activity, on the observed change of F in the upper stratosphere. Implications of the present findings and comparison with model results are discussed.

Zander, R.↗

NASA NTRS1999

Observation of Individual Fluorine Atom from Highly Oriented Poly (tetrafluoroethylene) Films by Atomic Force Microscopy

Direct observation of the film thickness, molecular structure and individual fluorine atoms from highly oriented poly(tetrafluoroethylene) (PTFE) films were achieved using atomic force microscopy (AFM). A thin PTFE film is mechanically deposited onto a smooth glass substrate at specific temperatures by a friction transfer technique. Atomic resolution images of these films show that the chain-like helical structures of the PTFE macromolecules are aligned parallel to each other with an intermolecular spacing of 5.72 A, and individual fluorine atoms are clearly observed along these twisted molecular chains with an interatomic spacing of 2.75 A. Furthermore, the first direct AFM measurements for the radius of the fluorine-helix, and of the carbon-helix in sub-angstrom scale are reported as 1.70 A and 0.54 A respectively.

Lee, Jonathan A.,↗

NASA NTRS2000

Observation of Individual Fluorine Atoms from Highly Oriented Poly(Tetrafluoroethylene) Films by Atomic Force Microscopy

Direct observation of the film thickness, molecular structure, and individual fluorine atoms from highly oriented poly(tetrafluoroethylene) (PTFE) films were achieved using atomic force microscopy (AFM). A thin PTFE film is mechanically deposited onto a smooth glass substrate at specific temperatures by a friction-transfer technique. Atomic resolution images of these films show that the chain-like helical structures of the PTFE macromolecules are aligned parallel to each other with an intermolecular spacing of 5.72 A, and individual fluorine atoms are clearly observed along these twisted molecular chains with an interatomic spacing of 2.75 A. Furthermore, the first direct AFM measurements for the radius of the fluorine-helix, and of the carbon-helix in sub-angstrom scale are reported as 1.7 and 0.54 A respectively.

Lee, J. A.↗

NASA NTRS1997

Relative rates for plasma homo- and copolymerizations of olefins in a homologous series of fluorinated ethylenes

It is well known that the rate of plasma polymerization, or deposition rate, of a given monomer depends on various plasma process parameters, e.g., monomer flow rate, pressure, power, frequency (DC, rf or microwave), location of the substrate in the reactor, reactor geometry or configuration, and temperature. In contrast, little work has been done to relate deposition rates to monomer structures for a homologous series of monomers where the rates are obtained under identical plasma process parameters. For the particular series of fluorinated ethylenes (C2HxF4-x; x = 0-4), deposition rates were reported for ethylene (ET), vinyl fluoride, vinylidene fluoride and tetrafluoroethylene (TFE), but for plasma polymerizations carried out under different discharge conditions, e.g., pressure, current density, and electrode temperature. Apparently, relative deposition rates were reported for only two members of that series (ET, x = 4, and TFE, x = 0) for which the plasma polymerizations were conducted under identical conditions. We now present relative deposition rates for both homopolymerizations and copolymerizations of the entire series of fluorinated ethylenes (x = 0-4). Our interest in such rates stems from prior work on the plasma copolymerization of ET and TFE in which it was found that the deposition rates for the plasma copolymers, when plotted versus mol % TFE in the ET/TFE feed stock, followed a concave-downward curve situated above the straight line joining the deposition rates for the plasma homopolymers. This type of plot (observed also for an argon-ET/TFE plasma copolymerization) indicated a positive interaction between ET and TFE such that each monomer apparently "sensitized" the plasma copolymerization of the other. Since the shape of that plot is not altered if mol % TFE is replaced by F/C, the fluorine-to-carbon ratio, this paper aims (1) to show how the relative deposition rates for plasma copolymers drawn from all pairs of monomers in the C2HxF4-x series, as well as the deposition rates for the individual plasma homopolymers, vary with F/C ratios of the monomers or monomer blends, and (2) to see if those rates give rise to a common plot.

NASA Center ARC↗

NASA NTRS2005

Friction Properties of Surface-Fluorinated Carbon Nanotubes

Surface modification of the tubular or sphere-shaped carbon nanoparticles through chemical treatment, e.g., fluorination, is expected to significantly affect their friction properties. In this study, a direct fluorination of the graphene-built tubular (single-walled carbon nanotubes) structures has been carried out to obtain a series of fluorinated nanotubes (fluoronanotubes) with variable C(n)F (n =2-20) stoichiometries. The friction coefficients for fluoronanotubes, as well as pristine and chemically cut nanotubes, were found to reach values as low as 0.002-0.07, according to evaluation tests run in contact with sapphire in air of about 40% relative humidity on a ball-on-disk tribometer which provided an unidirectional sliding friction motion. These preliminary results demonstrate ultra-low friction properties and show a promise in applications of surface modified nanocarbons as a solid lubricant.

Wal, R. L. Vander↗