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NASA NTRS1983

The effects of metals and inhibitors on thermal oxidative degradation reactions of unbranched perfluoroalkylethers

Thermal oxidative degradation studies were performed on unbranched perfluoroalkylethers at 288 C in oxygen. Metals and alloys studied included Ti, Al, and Ti (4 Al, 4 Mn). The mechanism of degradation was by chain scission. Ti and Al promoted less degradation than Ti (4 Al, 4 Mn). The two inhibitors investigated (a perfluorophenyl phosphine and a phosphatriazine) reduced degradation rates by several orders of magnitude. Both inhibitors were effective for the same duration (75 to 100 hours). The phosphatriazine appeared to provide more surface protection.

Jones, W. R., Jr.↗

NASA NTRS1983

HCN formation on Jupiter - The coupled photochemistry of ammonia and Acetylene

HCN formation in the upper troposphere and lower stratosphere of Jupiter is presently modeled in terms of UV pyrolysis of the C2H5N isomer aziridine, which is a product of the NH2 and C2H3 radicals that originate from ammonia photolysis and the addition of H atoms to acetylene, respectively. The sensitivity of the HCN column density to the individual rate constants and the eddy diffusion coefficient profile is considered, along with the possibility that additional HCN-yielding pathways may exist. Both ammonia and phosphine are strongly depleted by photolysis.

Kaye, J. A.↗

NASA NTRS1983

Elastomer-modified phosphorus-containing imide resins

Phosphine oxide-containing polyimide resins modified by elastomers, are disclosed which have improved mechanical properties. These products are particularly useful in the production of fiber or fabric-reinforced composites or laminates.

Varma, I. K.↗

NASA NTRS1984

Phosphorus-containing imide resins

Flame-resistant reinforced bodies are disclosed which are composed of reinforcing fibers, filaments or fabrics in a cured body of bis- and tris-imide resins derived from tris(m-aminophenyl) phosphine oxides by reaction with maleic anhydride or its derivatives, or of addition polymers of such imides, including a variant in which a mono-imide is condensed with a dianhydride and the product is treated with a further quantity of maleic anhydride.

Varma, I. K.↗

NASA NTRS1986

Analysis of a thioether lubricant by infrared Fourier microemission spectrophotometry

An infrared Fourier microemission spectrophotometer is used to obtain spectra (wavenumber range, 630 to 1230 0.1 cm) from microgram quantities of thioether lubricant samples deposited on aluminum foil. Infrared bands in the spectra are reproducible and could be identified as originating from aromatic species (1,3-disubstituted benzenes). Spectra from all samples (neat and formulated, used and unused) are very similar. Additives (an acid and a phosphinate) present in low concentration (0.10 percent) in the formulated fluid are not detected. This instrument appears to be a viable tool in helping to identify lubricant components separated by liquid chromatography.

Jones, W. R., Jr.↗

NASA NTRS1985

The photochemistry of the atmospheres of the outer planets and their satellites

The thermal structure and composition of Uranus, Neptune, Saturn, Jupiter, Titan, and Io are described. Molecular hydrogen is the dominant constituent in the atmosphere of the outer planets. The hydrogen and helium, methane, ammonia and phosphine, and carbon monoxide photochemical reactions of the outer planets are studied. The importance of Jupiter's lightning as a source of organic matter is examined. The aerosol and haze layers of the stratosphere of Jupiter, Saturn, Neptune, and Uranus are observed. The photochemistry of Titan's atmosphere, which includes nitrogen, methane, carbon monoxide, and carbon dioxide reactions, is analyzed. The SO2 atmosphere on Io is discussed.

Strobel, D. F.↗

NASA NTRS1985

Photochemistry and clouds of Jupiter, Saturn and Uranus

Photochemistry of ammonia, methane, phosphine, hydrogen sulfide, methylamine, hydrogen cyanide and carbon monoxide in the atmospheres of Jupiter, Saturn and Uranus is discussed. Condensation of ammonia, ammonium hydrosulfide, water, methane, ethane and acetylene below and near the tropopause of these planets is formulated. Whenever necessary, new calculations are included. Candidates for the upper atmospheric hazes, and the reddish-brown chromosphore in the clouds of Jupiter and Saturn are discussed.

Atreya, S. K.↗

NASA NTRS1985

The effects of metals and inhibitors on thermal oxidative degradation reactions of unbranched perfluoroalkyl ethers

Jones, W. R., Jr.↗

NASA NTRS1987

Laboratory evaluation and application of microwave absorption properties under simulated conditions for planetary atmospheres

Laboratory measurements were conducted to evaluate properties of atmospheric gases under simulated conditions for the outer planets. A significant addition to this effort was the capability to make such measurements at millimeter wavelengths. Measurements should soon be completed on the millimeter wave absorption from ammonia under Jovian conditions. Also studied will be the feasibility of measuring the microwave and millimeter wave properties of phosphine (PH3) under simulated Jovian conditions. Further analysis and application of the laboratory results to microwave and millimeter wave absorption data for the outer planet, such as Voyager Radio Occultation experiments, will be pursued.

Steffes, Paul G.↗

NASA NTRS1993

Organometallic chemical vapor deposition and characterization of ZnGeP2/GaP multiple heterostructures on GaP substrates

The growth of ZnGeP2/GaP double and multiple heterostructures on GaP substrates by organometallic chemical vapor deposition is reported. These epitaxial films were deposited at a temperature of 580 C using dimethylzinc, trimethylgallium, germane, and phosphine as source gases. With appropriate deposition conditions, mirror smooth epitaxial GaP/ZnGeP2 multiple heterostructures were obtained on (001) GaP substrates. Transmission electron microscopy (TEM) and secondary ion mass spectroscopy (SIMS) studies of the films showed that the interfaces are sharp and smooth. Etching study of the films showed dislocation density on the order of 5x10(exp 4)cm(sup -2). The growth rates of the GaP layers depend linearly on the flow rates of trimethylgallium. While the GaP layers crystallize in zinc-blende structure, the ZnGeP2 layers crystallize in the chalcopyrite structure as determined by (010) electron diffraction pattern. This is the first time that multiple heterostructures combining these two crystal structures were made.

Xing, G. C.↗

NASA NTRS1994

Detection of the 267 GHz J = 1-0 rotational transition of PH3 in Saturn with a new Fourier transform spectrometer

In recent observations at the Caltech Submillimeter Observatory, the highly pressure-broadened (FWHM = 11.2 GHz) J = 1-0 rotational transition of PH3 (phosphine) was detected on Saturn. By modeling the Saturnian atmosphere with a radiative transfer code, the observed line profile was consistent with a constant PH3 mole fraction of 3.0 plus or minus 1.0 ppm in the upper troposphere. A best-fit to the depth of the line implies a cutoff at high altitudes, with no PH3 present at pressures approximately less than 100 mbar. The observed line depth, combined with the lack of a detectable emission core, implies that a cutoff in the PH3 abundance occurs at a pressure between 13 and 140 mbar. PH3 in Jupiter was not detected, nor any other molecular lines between 195 and 295 GHz (1.54 mm and 1.02 mm, respectively) in either Jupiter or Saturn.

Weisstein, Eric W.↗

NASA NTRS1995

Enhancement of perfluoropolyether boundary lubrication performance: I. Preliminary results

A ball bearing simulator operating under starved conditions was used to evaluate the boundary lubrication performance of a perfluoropolyether (PFPE) Krytox 143 AB. Several approaches to enhance boundary lubrication were studied. These included: (1) soluble boundary additives, (2) bearing surface modifications, (3) 'run-in' surface films, and (4) ceramic bearing components. In addition, results were compared with two non-perfluorinated liquid lubricant formulations. Based on these preliminary tests, the following tentative conclusions can be made: (1) substantial improvements in boundary lubrication performance were observed with a beta-diketone boundary additive and a tricresyl phosphate (TCP) liquid surface pretreatment; (2) the use of rough Si3N4 balls (Ra = 40 micro-in) also provided substantial improvement but with concomitant abrasive wear; (3) marginal improvements were seen with two boundary additives (a phosphine and a phosphatriazine) and a neat (100%) fluid (a carboxylic acid terminated PFPE); and surface pretreatments with a synthetic hydrocarbon, a PTFE coating, and TiC coated 440C and smooth Si3N4 balls (R(sub a) less than 1 micro-in); and (4) two non-PFPE lubricant formulations (a PAO and a synthetic hydrocarbon) yielded substantial improvements.

Jones, W. R., Jr.↗

NASA NTRS1994

Detection of the 267 GHz J = 1-0 rotational transition of PH3 in Saturn with a new fourier transfer spectrometer

In recent observations with the Fourier transform spectrometer at the Caltech Submillimeter Observatory (CSO), we have detected the highly pressure-broadened (Full width at half maximum (FWHM) = 11.2 GHz) J = 1-0 rotational transition of PH3 (phosphine) on Saturn. By modeling the saturnian atmosphere with a radiative transfer code, we find that the observed line profile is consistent with a constant PH3 mole fraction of 0.3 +/- 1.0 ppm in the upper troposphere. A best fit to the depth of the line implies a cutoff at high altitudes, with no PH3 present at pressures less than and about 100 mbar. The observed line depth, combined with the lack of a detectable emission core, implies that a cutoff in the PH3 abundance occurs at a pressure between 13 and 140 mbar. We did not detect PH3 in Jupiter or any other molecular lines between 195 and 295 GHz (1.54 mm and 2.02 mm, respectively) in either Jupiter or Saturn.

Weisstein, Eric W.↗

NASA NTRS1995

P-polarized reflectance spectroscopy: A high sensitive real-time monitoring technique to study surface kinetics under steady state epitaxial deposition conditions

This paper describes the results of real-time optical monitoring of epitaxial growth processes by p-polarized reflectance spectroscopy (PRS) using a single wavelength application under pulsed chemical beam epitaxy (PCBE) condition. The high surface sensitivity of PRS allows the monitoring of submonolayer precursors coverage on the surface as shown for GaP homoepitaxy and GaP on Si heteroepitaxy as examples. In the case of heteroepitaxy, the growth rate and optical properties are revealed by PRS using interference oscillations as they occur during growth. Super-imposed on these interference oscillations, the PRS signal exhibits a fine structure caused by the periodic alteration of the surface chemistry by the pulsed supply of chemical precursors. This fine structure is modeled under conditions where the surface chemistry cycles between phosphorus supersaturated and phosphorus depleted surfaces. The mathematical model describes the fine structure using a surface layer that increases during the tertiarybutyl phosphine (TBP) supply and decreases during and after the triethylgallium (TEG) pulse, which increases the growing GaP film thickness. The imaginary part of the dielectric function of the surface layer is revealed from the turning points in the fine structure, where the optical response to the first precursor pulse in the cycle sequence changes sign. The amplitude of the fine structure is determined by the surface layer thickness and the complex dielectric functions for the surface layer with the underlying bulk film. Surface kinetic data can be obtained by analyzing the rise and decay transients of the fine structure.

Dietz, Nikolaus↗

NASA NTRS1996

Enhancement of Perfluoropolyether Boundary Lubrication Performance

A ball bearing simulator operating under starved conditions was used to perform screening tests to evaluate the boundary lubrication performance of a branched perfluoropolyether (PFPE), K-143 AB. Several approaches to enhance boundary lubrication were studied. These included: (1) soluble boundary additives, (2) bearing surface modifications, (3) 'run-in' surface films, and (4) ceramic bearing components. In addition, results were compared with two non-perfluorinated liquid lubricant formulations. Based on these tests, the following tentative conclusions can be made: (1) Substantial improvements in boundary lubrication performance were observed with a beta-diketone boundary additive and a tricresyl phosphate (TCP) liquid surface pretreatment, (2) the use of rough Si3N4 balls (R(sub a) = 40 micro-inch) also provided increases in test duration, but with concomitant abrasive wear, (3) moderate improvements were seen with two boundary additives (a phosphine and a phosphatriazine) and a neat (100%) fluid (a carboxylic acid terminated PFPE); and small improvements with surface pretreatments with synthetic hydrocarbons, a polytetrafluoroethylene (PTFE) coating, and TiC coated 440 C and smooth Si3N4 balls (R(sub a) = 1 micro-inch), and (4) two non-PFPE lubricant formulations (a polyalphaolefin (PAO) and synthetic hydrocarbon) yielded substantial improvements.

Jones, W. R., Jr.↗

NASA NTRS1996

Phospa-s-Triazines and Related Compositions of Improved Hydrolytic and Thermal Stability

The objective of the Program was to synthesize novel degradation inhibitors for perfluoropolyalkylether fluids and to evaluate their performance as well as that of other available inhibitors. Four novel additives: (C3F7OCF(CF3)CF2OC(CF3)2CN)((C6H5)2PN)2, (C3F7O(CF(CF3)CF2O)2C(CF3)2CN)((C6H5)2PN)2, u-(C3F7OCF(CF3)CF2OC(CF3)2CN)2((C6H5)2PN)2 and C3F7(OCF(CF3)CF2)6C6H4OP(O)(OC6H5)2 were prepared, characterized and their thermal stabilities established. The alloys studied were: 440C steel, M-50 steel, Pyrowear 675, Cronidur 30, Ti (4Al, 4Mn), and Ti (6Al, 4V). The additives and metals were evaluated in two different lots of Fomblin Z25, in Krytox 143AC and in Krytox 16256. Phosphate esters were found to be fully effective in arresting perfluoropolyaucylether fluid's degradation at temperatures up to 300 C over 24 h in the presence of alloys in oxygen. The overall rating of additives was: phosphates greater than phosphate/diester mixture greater than phosphine grater vthan or equal to phpospha-s-triazines.

Paciorek, K. J. L.↗

NASA NTRS1994

Chemistry of Star-Forming Cores

Chemical effects arising from the exchange of molecules between dust and gas in dense clumps are described. Selective desorption of CO and N2 from grains in cool cores can account for the presence of ammonia in several cores in the NGC 2024 cloud. Evaporation of ices containing methanol and ethanol can lead to detectable abundances of (C2H5)(sub 2)O and CH3OC2H5. Results are presented for the hot core chemistries of sulphur and phosphorus which are initiated by evaporated hydrogen sulphide and phosphine. The implications of these studies for understanding the nature of molecular mantles, the evolution of molecular complexity in the gas phase, and the presence of small-scale abundance gradients in star-forming regions, are briefly discussed.

Charnley, S. B.↗

NASA NTRS1997

Effect of Metal Alloys, Degradation Inhibitors, Temperatures on Thermal Oxidative Stability of CF3O(CF2O)(sub x)(CF2O)(sub y)CF3 Fluids

Degradation-promoting action of a series of ferrous and titanium alloys on CF3O(CF2O)(sub x)(CF2-CF2O)(sub y)CF3-based Z25 fluids and the inhibition effectiveness of several classes of additives were investigated. Four types of additives-phosphines, phosphates, phospha-s-triazines, and diphosphatetraazacyclooctatetraene-were studied in two batches of Z25 fluid, P28 and P151. In the absence of inhibitors, titanium alloys were more detrimental than the ferrous metals, but the additives were more effective in the presence of titanium alloys. Phosphate esters totally inhibited the decomposition of P151 at 330 C over 24 h in both types of alloys. The other additives were effective at lower temperatures. The responsiveness of fluid to an additive was found to be batch dependent.

Jones, William R., Jr.↗