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36 records · Page 2

Degradation of Perfluorinated Ether Lubricants on Pure Aluminum Surfaces: Semiempirical Quantum Chemical Modeling

The AM1 semiempirical quantum chemical method was used to model the interaction of perfluoroethers with aluminum surfaces. Perfluorodimethoxymethane and perfluorodimethyl ether were studied interacting with aluminum surfaces, which were modeled by a five-atom cluster and a nine-atom cluster. Interactions were studied for edge (high index) sites and top (low index) sites of the clusters. Both dissociative binding and nondissociative binding were found, with dissociative binding being stronger. The two different ethers bound and dissociated on the clusters in different ways: perfluorodimethoxymethane through its oxygen atoms, but perfluorodimethyl ether through its fluorine atoms. The acetal linkage of perfluorodimeth-oxymethane was the key structural feature of this molecule in its binding and dissociation on the aluminum surface models. The high-index sites of the clusters caused the dissociation of both ethers. These results are consistent with the experimental observation that perfluorinated ethers decompose in contact with sputtered aluminum surfaces.

Slaby, Scott M.↗

Lunar Dust Simulant Particle Adhesion on Copolyimide Alkyl Ethers

Mitigation of lunar dust contamination is one of the greatest challenges to be overcome to realize a sustained lunar presence. Likely solutions will integrate active mitigation strategies, requiring the input of external energy, and passive materials, exhibiting an intrinsic resistance to lunar dust adhesion. In this work, a series of copolyimide alkyl ethers containing per fluorinated side-chains were generated to evaluate the influence surface modification agents have on surface chemical, topographical, and mechanical properties. An expanded testing protocol to characterize the adhesion interaction between lunar dust simulant and the copolyimide substrate was carried out. The interfacial adhesion strength was in-situ measured by a custom-built particulate adhesion instrument, utilizing a sonic wand. Surface mechanical properties were characterized by nanoindentation, utilizing the continuous stiffness measurement approach. A nominal presence of surface modifying agents, 1 wt%, resulted in a six-fold reduction in adhesion strength of the interface. A strong inverse correlation between the adhesion strength and Young’s modulus of the substrate was identified. The reduction was attributed to a synergistic interaction between the surface energy, surface roughness, and modulus of the copolyimide alkyl ethers film.

Lunar Dust, Particulate Adhesion, Surface Migratio↗

Experimental and Calculational Studies of the Interactions of BF3 with Fluoroethers

BF3 was co-condensed with (C2H5)2O, (CF3CH2)2O and (C2F5)2O in excess argon at 15 K. Infrared spectra of the matrices showed a definite Lewis acid-base interaction between BF3 and diethyl ether; a weak but definite interaction with bis(2,2,2,-trifluorodiethyl)ether, and no observable interaction with perfluorodiethyl ether. Molecular orbital (MO) calculations complemented the experimental observations by revealing that fluorine atoms on the ethers decreased electron localization about the oxygen atom. Thus, the experimental data and MO calculations indicated a clear trend between strength of interaction with BF3 and the degree of ether F substitution. The implications of the results for commercial perfluoro ether lubricant/metal oxide surface interactions are discussed.

Zehe, Michael J.↗

Trifluoromethyl-substituted polymers

The synthesis of polymers is discussed. It includes: (1) the synthesis of fluorine-containing crosslinked poly(ether ketones); (2) the synthesis and characterization of poly(imide amides) and their N-methylated analogues; (3) the synthesis of fluorine-containing aromatic polyethers; (4) the synthesis of novel fluorine-containing aromatic polysiloxanes; and (5) the conversion of 6F-containing polythioethers to polysulfones. It is hoped that these polymers will find use as low dielectric materials in electronic applications, function as thermal control coatings, or be suitable elastomeric sealants for extreme service conditions.

Cassidy, Patrick E.↗

Theoretical and Experimental Determination of the Proton Affinity of (CF3CH2)2O

We report the experimental determination of the proton affinity of the molecule (CF3CH2)2O using chemical ionization mass spectrometry, and we compare it to the theoretical value obtained for protonation at the oxygen atom using the calculational methodology (MP2/6-31G**//MP2/3-21G). The proton affinity for this molecule as measured by bracketing experiments was between 724 kJ/mole and 741 kJ/mole. Ab initio (MP2/6-31G**//MP2/3-21G) calculations yield a value of about 729 kJ/mole, in agreement with the chemical ionization experiments. The results of these and related calculations suggest that the (MP2/6-31G**//MP2/3-21G) methodology is acceptable for estimating the proton affinities of partially-and fully-fluorinated methyl and ethyl ethers. We submit that any conclusions about the chemistry of fluoroether polymer lubricants based on their basicity can also be predicted reliably with such calculations.

Zehe, Michael J.↗

The preparation of new perfluoro ether fluids exhibiting excellent thermal-oxidative stabilities

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.

Jones, William R., Jr.↗

Radiation Durability of Candidate Polymer Films for the Next Generation Space Telescope Sunshield

The Next Generation Space Telescope (NGST), anticipated to be launched in 2009 for a 10-year mission, will make observations in the infrared portion of the spectrum to examine the origins and evolution of our universe. Because it must operate at cold temperatures in order to make these sensitive measurements, it will use a large, lightweight, deployable sunshield, comprised of several polymer film layers, to block heat and stray light. This paper describes laboratory radiation durability testing of candidate NGST sunshield polymer film materials. Samples of fluorinated polyimides CP1 and CP2, and a polvarylene ether benzimidazole. TOR-LM(TM), were exposed to 40 keV electron and 40 keV proton radiation followed by exposure to vacuum ultraviolet (VUV) radiation in the 115 to 200 nm wavelength range. Samples of these materials were also exposed to VUV without prior electron and proton exposure. Samples of polyimides Kapton HN, Kapton E, and Upilex-S were exposed to electrons and protons only, due to limited available exposure area in the VUV facility. Exposed samples were evaluated for changes in solar absorptance and thermal emittance and mechanical properties of ultimate tensile strength and elongation at failure. Data obtained are compared with previously published data for radiation durability testing of these polymer film materials.

Dever, Joyce↗

Syntheses and degradations of fluorinated heterocyclics

The relative stability of two ring systems, the triazine rings and 1,2,4-oxadiazoles, which offer potential crosslinks useful for curing perfluoroalkyl ether elastomers, has been investigated. Tris (perfluoro-n-heptyl)-s-triazine, the perfluoroether substituted-s-triazine, 1,4-bis/(5-perfluoro-n-heptyl)-1,2,4-oxadiazolyl/benzene, its perfluoroalkyl ether substituted analog, and 3,5-bis-(perfluoro-n-heptyl)-1,2,4-oxadiazole were synthesized and subjected to thermal and oxidative degradation at 235 and 325 C and to hydrolytic degradation at 235 C. The perfluoroalkyl ether substituted triazine and 3,5-bis(perfluoro-n-heptyl)-1,2,4-oxadiazole were found to be stable under all conditions investigated.

Paciorek, K. L.↗

Better PFAE's From Direct Fluorination

New low-molecular-weight perfluoroalkylethers (PFAE's) synthesized by direct fluorination in experimental study. Correlated viscosity and oxidation characteristics of PFAE's with structures to evaluate suitability as high-temperature lubricants and hydraulic fluids. Direct fluorination process attractive because it often involves single-step reaction and uses cheap starting materials. Versatile: produces highly branched ethers as well as polyethers containing more than two sequential carbon atoms in polymer chains. Such molecules cannot be made by conventional techniques.

Jones, W. R., Jr.↗

Exposure of Polymer Film Thermal Control Materials on the Materials International Space Station Experiment (MISSE)

Seventy-nine samples of polymer film thermal control (PFTC) materials have been provided by the National Aeronautics and Space Administration (NASA) Glenn Research Center (GRC) for exposure to the low Earth orbit environment on the exterior of the International Space Station (ISS) as part of the Materials International Space Station Experiment (MISSE). MISSE is a materials flight experiment sponsored by the Air Force Research Lab/Materials Lab and NASA. This paper will describe background, objectives, and configurations for the GRC PFTC samples for MISSE. These samples include polyimides, fluorinated polyimides, and Teflon fluorinated ethylene propylene (FEP) with and without second-surface metallizing layers and/or surface coatings. Also included are polyphenylene benzobisoxazole (PBO) and a polyarylene ether benzimidazole (TOR-LM). On August 16, 2001, astronauts installed passive experiment carriers (PECs) on the exterior of the ISS in which were located twenty-eight of the GRC PFTC samples for 1-year space exposure. MISSE PECs for 3-year exposure, which will contain fifty-one GRC PFTC samples, will be installed on the ISS at a later date. Once returned from the ISS, MISSE GRC PFTC samples will be examined for changes in optical and mechanical properties and atomic oxygen (AO) erosion. Additional sapphire witness samples located on the AO exposed trays will be examined for deposition of contaminants.

Dever, Joyce↗

New Fluorinated Polymers

This report summarizes progress during 1996 in our research effort along with a description of additional results associated with a TAG supplement to this grant (items 2 and 5 below). Progress is reported in five areas: 1) Polyamides Derived from [(p-HOOCC6H4)](sub 2)C(CF3)X (X= -CF3, OCH3, Cl); 2) Phosphorus-containing '12F-PEK' - Effect of Systematic Replacement of [(p-FC6H4COC6H4)](sub 2)C[(CF3)](sub 2) Monomer by [(p-FC6H4)](sub 2)(C6H5)PO; 3) Poly(ether ketone)s Derived from [(p-FC6H4COC6H4)](sub 2)(C6H5)PO; 4) New CF3-containing Organosilane Monomers and; 5) New Monomers for 12F-PEK Analogues with Improved Processability and Solubility.

Fitch, John W., III↗

X-ray Photoelectron Spectroscopy Study of Argon-Plasma-Treated Fluoropolymers

Films of poly(tetrafluoroethylene) (PTFE) and of a tetrafluoroethylene-perfluoroalkyl vinyl ether (approximately 49:1) copolymer (PFA) were exposed to a radio-frequency argon plasma and then examined by X-ray photoelectron spectroscopy (XPS). The use of fluoropolymer films nearly free of surface hydrocarbon contamination as well as the use of a monochromatized X-ray source for XPS removed two factors contributing to conflicting reports on the effect of exposure time on the fluorine-to-carbon (F/C) and oxygen-to-carbon (O/C) ratios for several Ar-plasma-treated fluoropolymers. Contrary to literature indications, a common pattern was found for PTFE and PFA: a moderate decrease in F/C ratio (from 1.99 to 1.40, and from 1.97 to 1.57, respectively), together with a moderate increase in O/C ratio (from negligible to about 0.10, and from 0.012 to about O.10, respectively) at very short exposures, after which the F/C ratios remained essentially constant on prolonged exposures, while the O/C ratios for PTFE and PFA leveled off at 0.11 and 0.15, respectively. The XPS C(sub 1s), spectra for these polymers exposed to the Ar plasma for 20 min were similar and presented, besides a prominent peak at 292.0 eV (CF2,) and a minor peak at 294.0 or 294.1 eV (CF3), a composite band of four curve-resolved peaks (approximately 285-290 eV) representing various CH, CC, CO, CN, and CF functionalities.

Golub, Morton A.↗

Wholly Aromatic Ether-Imides as n-Type Semiconductors

Some wholly aromatic ether-imides consisting of rod-shaped, relatively-low-mass molecules that can form liquid crystals have been investigated for potential utility as electron-donor-type (ntype) organic semiconductors. It is envisioned that after further research to improve understanding of their physical and chemical properties, compounds of this type would be used to make thin film semiconductor devices (e.g., photovoltaic cells and field-effect transistors) on flexible electronic-circuit substrates. This investigation was inspired by several prior developments: Poly(ether-imides) [PEIs] are a class of engineering plastics that have been used extensively in the form of films in a variety of electronic applications, including insulating layers, circuit boards, and low-permittivity coatings. Wholly aromatic PEIs containing naphthalene and perylene moieties have been shown to be useful as electrochromic polymers. More recently, low-molecular-weight imides comprising naphthalene-based molecules with terminal fluorinated tails were shown to be useful as n-type organic semiconductors in such devices as field-effect transistors and Schottky diodes. Poly(etherimide)s as structural resins have been extensively investigated at NASA Langley Research Center for over 30 years. More recently, the need for multi-functional materials has become increasingly important. This n-type semiconductor illustrates the scope of current work towards new families of PEIs that not only can be used as structural resins for carbon-fiber reinforced composites, but also can function as sensors. Such a multi-functional material would permit so-called in-situ health monitoring of composite structures during service. The work presented here demonstrates that parts of the PEI backbone can be used as an n-type semiconductor with such materials being sensitive to damage, temperature, stress, and pressure. In the near future, multi-functional or "smart" composite structures are envisioned to be able to communicate such important parameters to the flight crew and provide vital information with respect to the operational status of their aircraft.

Weiser, Erik↗

Synthesis, Characterization and Evaluation of Urethane Co-Oligomers Containing Pendant Fluoroalkyl Ether Groups

Coatings with the ability to minimize adhesion of insect residue and other debris are of great interest for future aircraft. These aircraft will exhibit increased fuel efficiency by maintaining natural laminar flow over greater wing chord distances. Successful coatings will mitigate the adhesion of debris on laminar flow surfaces that could cause a premature transition to turbulent flow. The use of surface modifying agents (SMA) that thermodynamically orient towards the air side of a coating can provide specific surface chemistry that may lead to a reduction of contaminate adhesion. Aluminum surfaces coated with urethane co-oligomers containing various amounts of pendant fluoroalkyl ether groups were prepared, characterized and tested for their abhesive properties. The coated surfaces were subjected to controlled impacts with wingless fruit flies (drosophila melanogaster) using both a benchtop wind tunnel and a larger-scale wind tunnel test facility. Insect impacts were recorded and analyzed using high-speed digital photography and the remaining residues characterized using optical surface profilometry and compared to that of an aluminum control. It was determined that using fluorinated oligomers to chemically modify coating surfaces altered the adhesion properties relative to the adhesion of insect residues to the surface.

Jereme R Doss↗

Acidic attack of perfluorinated alkyl ether lubricant molecules by metal oxide surfaces

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.

Zehe, Michael J.↗

Acidic attack of perfluorinated alkyl ether lubricant molecules by metal oxide surfaces

The reactions of linear perfluoropolyalkylether (PFAE) lubricants with alpha-Fe203 and Fe203-based solid superacids were studied. The reaction with alpha-Fe203 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 initial breakdown step was performed using alpha-Fe203, alpha-Fe203 preconverted to FeF3, and sulfate-promoted alpha-Fe203 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.

Zehe, Michael J.↗

Electrolytes for Low-Temperature Operation of Li-CFx Cells

A report describes a study of electrolyte compositions selected as candidates for improving the low-temperature performances of primary electrochemical cells that contain lithium anodes and fluorinated carbonaceous (CFx) cathodes. This study complements the developments reported in Additive for Low-Temperature Operation of Li-(CF)n Cells (NPO- 43579) and Li/CFx Cells Optimized for Low-Temperature Operation (NPO- 43585), which appear elsewhere in this issue of NASA Tech Briefs. Similar to lithium-based electrolytes described in several previous NASA Tech Briefs articles, each of these electrolytes consisted of a lithium salt dissolved in a nonaqueous solvent mixture. Each such mixture consisted of two or more of the following ingredients: propylene carbonate (PC); 1,2-dimethoxyethane (DME); trifluoropropylene carbonate; bis(2,2,2-trifluoroethyl) ether; diethyl carbonate; dimethyl carbonate; and ethyl methyl carbonate. The report describes the physical and chemical principles underlying the selection of the compositions (which were not optimized) and presents results of preliminary tests made to determine effects of the compositions upon the low-temperature capabilities of Li-CFx cells, relative to a baseline composition of LiBF4 at a concentration of 1.0 M in a solvent comprising equal volume parts of PC and DME.

Smart, Marshall C.↗