SEARCH · Engineering Papers
Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.
Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.
Coating of carbon tetrafluoride formed on interior surface of atomic-hydrogen maser by allowing gas to freeze on surface. New coating enables maser to oscillate down to 26 K; most effective previous coating, fluorinated ethylene/polypropylene (FEP) copolymer allowed oscillation down to about 50 K.
Containerless high temperature processing and material property measurements are discussed. Researchers developed methods for non-contact suspension, heating, and property measurement for materials at temperatures up to 3,680K, the melting point of tungsten. New, scientifically interesting results were obtained in Earth-based research. These results and the demonstration of new methods and techniques form a basis for further advances under the low gravity environment of space where containerless conditions are more easily achieved. Containerless high temperature material property investigations that have been completed in this and our earlier projects include measurements of fluorine LaB sub 6 reaction kinetics at 1,000 to 1,500K; optical property measurements on sapphire (Al2O3) at temperatures up to the melting point (2,327K); and vapor pressure measurements for LaB sub 6 at 2,000 to 2,500K, for molybdenum up to 2,890K and for tungsten up to 3,680K. Gas jet levitation which is applicable to any solid material, and electromagnetic levitation of electrical conductors were used to suspend the materials of interest. Non-contact heating and property measurements were achieved by optical techniques, i.e., laser heating, laser induced fluorescence measurements of vapor concentrations, and optical pyrometry for specimen temperatures.
An explanation of the relative resistance of various materials to attack by atomic oxygen is presented. Data from both ground based and on-orbit experiments is interpreted. The results indicate the importance of bond strengths, size and structure of pendant groups, and fluorination to the resistance of certain polymers to atomic oxygen. A theory which provides a partial explanation of the degradation of materials in low Earth orbit due to surface recombination of oxygen atoms is also included. Finally, a section commenting on mechanisms of material degradation is provided.
The first spectroscopic observation of CH in the a 4Sigma(0-) state are reported. The molecule was generated in a discharge-flow system in the reaction betweeen fluorine atoms and methane or between oxygen atoms and acetylene at a total pressure of about 1 Torr. Several resonances associated with the N = 1 - 0 transitions of 4Sigma(-) CH were observed at three separate laser wavelengths, while those for the N = 2 - 1 transition were observed at two wavelengths. Each observed Zeeman component consists of a well-split doublet arising from proton hyperfine structure. The reasons for assigning the observations to CH in its a 4Sigma(-) state are discussed.
Graphite fluoride fiber/polymer composite materials consist of graphite fluoride fibers in epoxy, polytetrafluoroethylene, or polyimide resin. Combines high electrical resistivity with high thermal conductivity and solves heat-transfer problems of many electrical systems. Commercially available in powder form, for use as dry lubricant or cathode material in lithium batteries. Produced by direct fluorination of graphite powder at temperature of 400 to 650 degree C. Applications include printed-circuit boards for high-density power electronics, insulators for magnetic-field cores like those found in alternators and transformers, substrates for thin-film resistors, and electrical-protection layers in aircraft de-icers.
Several microfabrication techniques combined into process cutting slots 100 micrometer long and 1 to 5 micrometer wide into tungsten dispenser cathodes for traveling-wave tubes. Patterned photoresist serves as mask for etching underlying aluminum. Chemically-assisted ion-beam etching with chlorine removes exposed parts of aluminum layer. Etching with fluorine or chlorine trifluoride removes tungsten not masked by aluminum layer. Slots enable more-uniform low-work function coating dispensed to electron-emitting surface. Emission of electrons therefore becomes more uniform over cathode surface.
The reactions of linear perfluoropolyalkylether (PFAE) lubricants with alpha-Fe2O3 and Fe2O3-based solid superacids were studied. The reaction with alpha-Fe2O3 proceeds in two stages. The first stage is an initial slow catalytic decomposition of the fluid. This reaction releases reactive gaseous products which attach the metal oxide and convert it to FeF3. The second stage is a more rapid decomposition of the fluid, effected by the surface FeF3. A study of the inital breakdown step was performed using alpha-Fe2O3, alpha-Fe2O3 preconverted to FeF3, and sulfate-promoted alpha-Fe2O3 superacids. The results indicate that the breakdown reaction involves acidic attack at fluorine atoms on acetal carbons in the linear PFAE. Possible approaches to combat the problem are outlined.
A study was performed with the objective of developing matrix resins that exhibit improved thermo-oxidative stability over state-of-the-art high temperature resins for use at temperatures up to 644 K (700 F) and air pressures up to 0.7 MPa (100 psia). The work was based upon a TRW discovered family of polyimides currently licensed to and marketed by Ethyl Corporation as EYMYD(R) resins. The approach investigated to provide improved thermo-oxidative properties was to use halogenated derivatives of the diamine, 2, 2-bis (4-(4-aminophenoxy)phenyl) hexafluoropropane (4-BDAF). Polyimide neat resins and Celion(R) 12,000 composites prepared from fluorine substituted 4-BDAF demonstrated unexpectedly lower glass transition temperatures (Tg) and thermo-oxidative stabilities than the baseline 4-BDAF/PMDA polymer.
In most instances separate electrocatalysts are needed to promote the reduction of O2 in the fuel cell mode and to generate O2 in the energy storage-water electrolysis mode in aqueous electrochemical systems operating at low and moderate temperatures (T greater than or equal to 200 C). Interesting exceptions are the lead and bismuth ruthenate pyrochlores in alkaline electrolytes. These catalysts on high area carbon supports have high catalytic activity for both O2 reduction and generation (1,2). Rotating ring-disk electrode measurements provide evidence that the O2 reduction proceeds by a parallel four-electron pathway. The ruthenates can also be used as self-supported catalysts to avoid the problems associated with carbon oxidation, but the electrode performance so far achieved in the research at Case Western Reserve University (CWRU) is considerably less. At the potentials involved in the anodic mode the ruthenate pyrochlores have substantial equilibrium solubility in concentrated alkaline electrolyte. This results in the loss of catalyst into the bulk solution and a decline in catalytic activity. Furthermore, the hydrogen generation counter electrode may become contaminated with reduction products from the pyrochlores (lead, ruthenium). A possible approach to this problem is to immobilize the pyrochlore catalyst within an ionic-conducting solid polymer, which would replace the fluid electrolyte within the porous gas diffusion O2 electrode. For bulk alkaline electrolyte, an anion-exchange polymer is needed with a transference number close to unity for the Oh(-) ion. Preliminary short-term measurements with lead ruthenates using a commercially available partially-fluorinated anion-exchange membrane as an overlayer on the porous gas-fed electrode indicate lower anodic polarization and virtually unchanged cathodic polarization.
Reactions of perfluoroalkylpolyethers (PFPE: Fomblin, Demnum and Krytox) were studied during the sliding contact of stainless steel specimens under ultrahigh vacuum conditions. All three fluids reacted with the steel specimens during sliding. Fomblin, which has acetal linkages, decomposed under the sliding conditions generating gaseous products, (COF2 and fluorinated carbons) which were detected by a quadrupole mass spectrometer. Gaseous products were not detected for the Demnum and Krytox fluids. The amount of gaseous products from Fomblin increased with increasing sliding speed. At the end of the sliding experiments, the wear scar and deposits on the specimens were examined by small spot size XPS. The oxide layer on the specimen surface was removed during sliding, and metal fluorides were formed on the worn surface. The surface of the wear scar and deposits were covered with adsorbed PFPE. Based on these results, it was concluded that the decomposition reaction on Fomblin was initiated by contacting the fluid with a fresh metal surface which was formed during sliding.
A series of low molecular weight perfluoroalkyl ethers (PFAEs) were synthesized by direct fluorination. Viscosity-temperature properties and oxidation stabilities were determined. Viscosity-temperature correlations indicated that increases in branching and increases in the size of the branching substituent caused a deterioration in viscometric properties (i.e., an increase in ASTM slope). In addition, increasing the ratio of carbon to oxygen in these compounds also increased the ASTM slope. Preliminary oxidation stability measurements indicated that highly branched PFAE fluids (i.e., those containing quaternary carbons) may be less stable than either those containing a single trifluoromethyl pendant group or those containing no branching at all.
This paper describes the damage structure induced in natural CaF2 by the electron beam when using TEM. The observed 10-20 nm periodic features with coherent fringe patterns and the pronounced loss of fluorine found after the TEM exposure of 100-line-oriented and 111-oriented sections of CaF2 provides support for the mechanism of damage by decomposition of CaF2 into 2F and Ca, with the Ca precipitates maintaining a close topotaxial relationship with the parent CaF2.
A nonmass-dependent sulfur isotope effect is present in the rotationally symmetric S2F10 molecule, produced in an electrical discharge through sulfur tetrafluoride. A similar isotopic fractionation was observed in the product S2F10 from the electrodissociation of SF5Cl and in the reaction between fluorine atoms produced by F2 photolysis and SF2, collectively ruling out the SF5 formation process as the source of the mass-independent fractionation. The secondary dissociation of S2F10 as a source of the mass-independent fractionation is ruled out by control S2F10 dissociation experiments which are shown to produce small mass-dependent fractionations. Mass-dependent effects such as sulfur isotopic exchange and secondary dissociation reactions are significant processes for the system under study, and have been quantitatively accounted for. The role of symmetry in nonmass-dependent isotope effects is strengthened by the present experiments, and the search and characterization of mass-independent effects is extended to sulfur-containing molecules.
The fifth year of the Center for Advanced Materials was marked primarily by the significant scientific accomplishments of the research programs. The Electronics Materials program continued its work on the growth and characterization of gallium arsenide crystals, and the development of theories to understand the nature and distribution of defects in the crystals. The High Tc Superconductivity Program continued to make significant contributions to the field in theoretical and experimental work on both bulk materials and thin films and devices. The Ceramic Processing group developed a new technique for cladding YBCO superconductors for high current applications in work with the Electric Power Research Institute. The Polymers and Composites program published a number of important studies involving atomistic simulations of polymer surfaces with excellent correlations to experimental results. The new Enzymatic Synthesis of Materials project produced its first fluorinated polymers and successfully began engineering enzymes designed for materials synthesis. The structural Materials Program continued work on novel alloys, development of processing methods for advanced ceramics, and characterization of mechanical properties of these materials, including the newly documented characterization of cyclic fatigue crack propagation behavior in toughened ceramics. Finally, the Surface Science and Catalysis program made significant contributions to the understanding of microporous catalysts and the nature of surface structures and interface compounds.
Thermosetting fluoropolymer foams are made by mixing fluid form thermosetting fluoropolymer components having a substantial fluorine content, placing the mixture in a pressure tight chamber, filling the chamber with a gas, at relatively low pressure, that is unreactive with the fluoropolymer components, allowing the mixture to gel, removing the gelled fluoropolymer from the chamber and thereafter heating the fluoropolymer at a relatively low temperature to simultaneously sure and foam the fluoropolymer. The resulting fluoropolymer product is closed celled with the cells storing the gas employed for foaming. The fluoropolymer resins employed may be any thermosetting fluoropolymer including fluoroepoxies, fluoropolyurethanes and fluoroacrylates.
NASA-Langley studies of polymer structure-property relationships have led to the development of a method for the reduction of dielectric constants in polyimides through chemical alterations of polymer backbone composition to reduce chain-chain electronic interactions, as well as through the incorporation of fluorine atoms into the polymer molecular structure. Still-greater dielectric constant reductions are obtainable by means of a physical incorporation of diamic acid additives into these low-dielectric polyimide systems; the resulting thermoplastic resins are applicable to polymer matrices for composite structural materials.
Both Tl2Ca2Ba2Cu3O10 and TlCa3BaCu3O8.5 are investigated for superconductivity as a function of the sintering temperature, time, atmosphere, and quench rate in an effort to synthesize the high-Tc superconducting phase in the thallium system. The samples are characterized by electrical resistivity measurements, X-ray diffraction, and scanning electron microscopy. Samples of starting composition Tl2Ca2Ba2Cu3O10 fired in air at 860-900 C and rapidly quenched show a Tc of 96-107 K. In contrast, specimens of starting composition TlCa3BaCu3O8.5 when baked at 900 C and slowly cooled in oxygen superconduct at 116 K and above and consist of Tl2Ca2Ba2Cu3O(10+x) as the dominant phase. The results also show that, in contrast to the case of YBa2Cu3O(7-x), doping with a small concentration of fluorine sharpens the resistive transition and produces a large Tc increase in thallium-based superconductors.
Reactions of perfluoroalkylpolyethers (PFPE: Fomblin, Demnum and Krytox) were studied during the sliding contact of stainless steel specimens under ultrahigh vacuum conditions. All three fluids reacted with the steel specimens during sliding. Fomblin, which has acetal linkages, decomposed under the sliding conditions generating gaseous products, (COF2 and fluorinated carbons) which were detected by a quadrupole mass spectrometer. Gaseous products were not detected for the Demnum and Krytox fluids. The amount of gaseous products from Fomblin increased with increasing sliding speed. At the end of the sliding experiments, the wear scar and deposits on the specimens were examined by small spot size XPS. The oxide layer on the specimen surface was removed during sliding, and metal fluorides were formed on the worn surface. The surface of the wear scar and deposits were covered with adsorbed PFPE. Based on these results, it was concluded that the decomposition reaction on Fomblin was initiated by contacting the fluid with a fresh metal surface which was formed during sliding.