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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.↗

Ferric chloride graphite intercalation compounds prepared from graphite fluoride

The reaction between graphite fluoride and ferric chloride was observed in the temperature range of 300 to 400 C. The graphite fluorides used for this reaction have an sp3 electronic structure and are electrical insulators. They can be made by fluorinating either carbon fibers or powder having various degrees of graphitization. Reaction is fast and spontaneous and can occur in the presence of air. The ferric chloride does not have to be predried. The products have an sp2 electronic structure and are electrical conductors. They contain first stage FeCl3 intercalated graphite. Some of the products contain FeCl2*2H2O, others contain FeF3 in concentrations that depend on the intercalation condition. The graphite intercalated compounds (GIC) deintercalated slowly in air at room temperature, but deintercalated quickly and completely at 370 C. Deintercalation is accompanied by the disappearing of iron halides and the formation of rust (hematite) distributed unevenly on the fiber surface. When heated to 400 C in pure N2 (99.99 vol %), this new GIC deintercalates without losing its molecular structure. However, when the compounds are heated to 800 C in quartz tube, they lost most of its halogen atoms and formed iron oxides (other than hematite), distributed evenly in or on the fiber. This iron-oxide-covered fiber may be useful in making carbon-fiber/ceramic-matrix composites with strong bonding at the fiber-ceramic interface.

Hung, Ching-Cheh↗

Fabrication of Iron-Containing Carbon Materials From Graphite Fluoride

Carbon materials containing iron alloy, iron metal, iron oxide or iron halide were fabricated. Typical samples of these metals were estimated to contain 1 iron atom per 3.5 to 5 carbon atoms. Those carbon materials containing iron alloy, iron metal, and/or Fe3O4 were magnetic. The kinetics of the fabrication process were studied by exposing graphite fluoride (CF(0.68)) to FeCl3 over a 280 to 420 C temperature range. Between 280 and 295 C, FeCl3 quickly entered the structure of CF(0.68), broke the carbon-fluorine bonds, and within 10 to 30 min, completely converted it to carbon made up of graphite planes between which particles of crystalline FeF3 and noncrystalline FeCl3 were located. Longer reaction times (e.g., 28 hr) or higher reaction temperatures (e.g., 420 C) produced materials containing graphite, a FeCl3-graphite intercalation compound, FeCl2(center dot)4H2O, and FeCl2(center dot)2H2O. These products were further heat treated to produce iron-containing carbon materials. When the heating temperature was kept in the 750 to 850 C range, and the oxygen supply was kept at the optimum level, the iron halides in the carbon structure were converted to iron oxides. Raising the heat to temperatures higher than 900 C reduced such iron oxides to iron metal. The kinetics of these reactions were used to suggest processes for fabricating carbon materials containing iron alloy. Such processes were then tested experimentally. In one of the successful trial runs, commercially purchased CF(0.7) powder was used as the reactant, and NiO was added during the final heating to 1200 C as a source of both nickel and oxygen. The product thus obtained was magnetic and was confirmed to be a nickel-iron alloy in carbon.

Hung, Ching-cheh↗

Ferrix Chloride-Graphite Intercalation Compounds Prepared From Graphite Flouride

The reaction between graphite fluoride and ferric chloride was observed in the temperature range of 300 to 400 C. The graphite fluorides used for this reaction have an sp(sup 3) electronic structure and are electrical insulators. They can be made by fluorinating either carbon fibers or powder having various degrees of graphitization. Reaction is fast and spontaneous and can occur in the presence of air. The ferric chloride does not have to be predried. The products have an sp(sup 2) electronic structure and are electrical conductors. They contain first-stage FeCl3 intercalated graphite. Some of the products contain FeCl2 (center dot) 2H2O, others contain FeF3, in concentrations that depend on the intercalation condition. The graphite intercalated compounds (GIC) deintercalated slowly in air at room temperature, but deintercalated quickly and completely at 370 C. Deintercalation is accompanied by the disappearance of iron halides and the formation of rust (hematite) distributed unevenly on the fiber surface. When heated to 400 C in pure N2 (99.99 vol%), this new GIC deintercalates without losing its molecular structure. However, when the compounds are exposed to 800 C N2, in a quartz tube, they lost most of their halogen atoms and formed iron oxides (other than hematite), distributed evenly in or on the fiber.

Hung, Ching-Cheh↗