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Nakahara, J. H.

Publications and source records attributed to Nakahara, J. H..

Improved perfluoroalkylether fluid development

The objective of this program was to optimize and scale up the linear perfluoroalkylether stabilization process and to provide test data regarding the fluids' thermal oxidative stability in the presence of metal alloys. The stabilization of Fomblin Z-25 was scaled up to 300 g of fluid. The modified fluid was stable at 316 C in oxygen in the presence of M-50 alloy for more than 24 hrs but less than 40 hrs; the amount of volatiles produced after 24 hrs was 5.5 mg/g. In the presence of Ti(4Al,4Mn) alloy, under the above conditions, following an exposure of 24 hrs, the amount of volatiles formed was 6.2 mg/g; 56 hrs exposure yielded 13.9 mg/g. The commercial fluid at 288 C (in oxygen) in the presence of M-50 after 15 hrs of exposure decomposed extensively, 342 mg/g; in the presence of Ti(4Al,4Mn) alloy after only 8 hrs at 288 C, the amount of volatiles was 191 mg/g. Formulation of the commercial fluid with C2PN3 additive was not as effective as the stabilization processing. All the perfluoroalkylether fluids studied were stable in nitrogen at 343 C. The thermal oxidative stability in the absence of metal alloys varied, with Aflunox exhibiting the best behavior. All the fluids were degraded in oxygen at 316 C during 24 hrs exposure to Ti(4Al,4Mn) alloy with the exception of a perfluoroalkylether substituted triazine and the modified Z-25.

Paciorek, K. L.

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

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.

Synthesis of perfluoroalkylene aromatic diamines

Analogues of methylene dianilines were synthesized, in which the methylene group between the two aromatic nuclei was replaced by various perfluoroalkylene linkage. The hydrolytic thermal, and thermal oxidative stabilities of PMR Polyimides derived from these diamines were determined. Three types of PMR Polyimide discs were fabricated from the dimethyl ester of 3,3', 4,4'-benzophenonetetracarboxylic acid, the methyl ester of 5-norbornene-2,3-dicarboxylic acid, and one of the following three diamines: methyl dianiline, 1,3-bis(4-aminophenyl)hexafluoropropane, and 2,2-bis(4-aminophenyl)hexafluoropropane. The polyimide based on 2,2-bis(4-aminophenyl)hexafluoropropane exhibited the best hydrolytic, thermal, and thermal oxidative stability as determined by moisture uptake and thermogravimetric analysis.

Paciorek, K. L.

Cross Linking and Degradation Mechanisms in Model Sealant Candidates

Model compounds were investigated as to which type of heterocyclic ring is the most advantageous for curing sealants based on perfluoroalkylether chains. The relative thermal, thermal oxidative, hydrolytic, and fuel stability of potential crosslinks were determined. Specifically substituted materials were synthesized and evaluation of their stabilities in air, inert atmosphere, water, and Jet-A fuel at 235 and 325 C was made. Three heterocyclic ring systems were considered, namely, triazine, 1,2,4- and 1,3,4-oxadiazoles.

Paciorek, K. L.

Syntheses and Degradations of Fluorinated Heterocyclics: Perfluoroalkyl and Perfluoroalkylether-1,3,4-Oxadiazoles - 3

2,5-Bis(perfluoro-n-heptyl)-, 2-perfluoroalkylether-5-perfluoro-n- heptyl- , and 2 , 5-bisperfluoroalkylether-1,3,4-oxadiazoles were synthesized and characterized. 2,5-Bis(perfluoro-n-heptyl)-1,3,4-oxadiazole was thermally and hydrolytically stable at 325 C; however, in the presence of air, degradation took place at 235 C. The perfluoroalkylether analogue exhibited thermal and hydrolytic stability at 325 C; it was found to be unaffected by jet-A fuel and air at 235 C. At 325 C in air some degradation occurred as evidenced by volatiles production, oxygen consumption, and 96% starting material recovery.

Paciorek, K. J. L.

Syntheses and Degradations of Fluorinated Heterocyclics: Perfluoroalkyl and Perfluroalkylether-1,2,4-Oxadiazoles - 2

3-Perfluoroalkylether-5-perfluoro-n-heptyl-1,2,4-oxadiazole and 3,S-bis(perfluoroalkylether)-1,2,4-oxadiazole were synthesized and characterized. The 3, 5-bis(perfluoroalkylether)-l, 2,4-oxadiazole was subjected to thermal, thermal oxidative, and hydrolytic degradations at 235 and 325 C and was found to be stable under these conditions as evidenced by practically quantitative recovery of the test samples. In the presence of Jet-A fuel at 235 C a low degree of degradation, approximately 4%, was observed. 3,5-Bis(perfluoro-n-heptyl)-1,2,4-oxadiazole was found to be stable to attack by water at 325 C; however in air in the presence of jet-A at 235 C the extent of degradation was in excess of 10%.

Paciorek, K. J. L.