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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.

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At least 19 records

The effects of aniline impurities on monopropellant hydrazine thruster performance

Both a 0.45-N and a 0.9-N thruster representative of the designs being flown on 3-axis stabilized spacecraft were used in testing various grades of hydrazine for the phenomenon of monopropellant hydrazine thruster catalyst bed poisoning. Both designs employed Shell 405 ABSG spontaneous catalyst. It is found that pulse shape distortion can be minimized, if not eliminated, by using aniline-free hydrazine. The mechanisms for both steady-state and pulse-mode performance loss are associated with the formation of a catalyst coke similar to the polycyclic aromatic poisons encountered in the petroleum industry. These poisoning mechanisms are reversible, with high-temperature operation being required to drive off the aniline coke deposits. It is recommended that a purified-grade hydrazine be considered for any mission that imposes operational conditions on a thruster which can result in aniline-induced poisoning of the catalyst bed.

Holcomb, L.↗

A common modality of action of simulated space stresses on the oxidative metabolism of ethylmorphine, aniline and p-nitroanisole by male rat liver.

High gravity, cold and starvation elicited similar responses in male Simonson rats. These responses included a decreased rate in body weight gain, increased metabolism of aniline and p-nitroanisole, and no consistent pattern of change in the metabolism of ethylmorphine. Cold and starvation increased the amount of hepatic cytochrome P-450, while hypobaric-hyperoxia caused no change in any of the parameters measured. When 1% acetone was given to the rats in their drinking water, the effects on drug metabolism were similar to those produced by food restriction in that the metabolism of aniline and p-nitroanisole was increased, and the metabolism of ethylmorphine unchanged. The type I binding spectrum of acetone suggests that it is either a substrate, inhibitor, or both for hepatitic oxidative enzymes.

Furner, R. L.↗

Site Alteration Effects from Rocket Exhaust Impingement During a Simulated Viking Mars Landing. Part 2: Chemical and Biological Site Alteration

Chemical and biological alteration of a Mars landing site was investigated experimentally and analytically. The experimental testing was conducted using a specially designed multiple nozzle configuration consisting of 18 small bell nozzles. The chemical test results indicate that an engine using standard hydrazine fuel will contaminate the landing site with ammonia (50-500ppm), nitrogen (5-50ppm), aniline (0.01-0.5ppm), hydrogen cyanide (0.01-0.5ppm), and water. A purified fuel, with impurities (mostly aniline) reduced by a factor of 50-100, limits the amount of hydrogen cyanide and aniline to below detectable limits for the Viking science investigations and leaves the amounts of ammonia, nitrogen, and water in the soil unchanged. The large amounts of ammonia trapped in the soil will make interpretation of the organic analysis investigation results more difficult. The biological tests indicate that the combined effects of plume gases, surface heating, surface erosion, and gas composition resulting from the retrorockets will not interfere with the Viking biology investigation.

Husted, R. R.↗

Synthesis of perfluoroalkylene dianilines

The objective of this contrast was to optimize and scale-up the synthesis of 2,2-bis(4-aminophenyl)-hexafluoropropane and 1,3-bis(4-aminophenyl)hexafluoropropane, as well as to explore avenues to other perfluoroalkyl-bridged dianilines. Routes other than Friedel-Crafts reaction leading to 2,2-bis(4-aminophenyl)hexafluoropropane were investigated. The processes utilizing bisphenol-AF were all unsuccessful; reactions aimed at the production of 4-(hexafluoro-2-halo-isopropyl)aniline from the hydroxyl intermediate failed to yield the desired products. Tailoring the conditions of the Friedel-Crafts reaction of 4-(hexafluoro-2-hydroxyisopropyl)aniline, aniline, and aluminum chloride by using hydrochloride salts and selecting optimum reagent ratios, reaction times, and temperature resulted in approx. 20% yield of pure crystallized 2,2-bis(4-aminophenyl)hexafluoropropane in 0.2 mole reaction batches. Yields up to approx. 40% were realized in small, approx. 0.01 mole, batches. The synthesis of 1,3-bis(4-aminophenyl)hexafluoropropane starting with perfluoroglutarimidine was reinvestigated. The yield of the 4-step reaction sequence giving 1,3-bis(4-acetamidophenyl)hexafluoropropane was raised to 44%. The yield of the subsequent hydrolysis process was improved by a factor of approx. 2. Approaches to prepare other perfluoroalkyl-bridged dianilines were unsuccessful. Reactions reported to proceed readily with trifluoromethyl substituents failed when longer chain perfluoroalkyl groups were employed.

Paciorek, K. L.↗

Net Heat of Combustion of AN-F-28 Aviation Gasolines

Experimental data on the heats of combustion and hydrogen contents of a number of aviation gasolines have been used in deriving a formula for computing net heat of combustion from (measured) gross heat of combustion. This formula appears to be sufficiently reliable for the purpose and has the advantage of making hydrogen determinations unnecessary. The data on heats of combustion are presented in tabular form, and in graphs showing the relation between net heat of combustion and (1) hydrogen content, (2) aniline point, (3) APO gravity, and (4) the product of aniline point and APO gravity. Data are given on the change in aniline point with time, and also the change resulting from the addition of xylidine.

FUELS - COMBUSTION TEMPERATURES↗

The synthesis of conducting polymers for corrosion prevention

The formation of an electrically conducting form of polyaniline by the oxidative polymerization of aniline was studied. Optimum yield and conductivities were obtained by treating aniline in 2 molar hydrochloric acid at 0 to 5 C with ammonium persulfate in 1.15 mole ratio. The yield was 37.6 percent of theory and the conductivity of the product was 10.5 S/cm. This material was formulated into epoxy and acrylic coatings which were also electrically conductive.

Mattson, Guy C.↗

Substituted 1,1,1-triaryl-2,2,2-trifluoroethanes and processes for their synthesis

Synthetic procedures are disclosed for tetraalkyls, tetraacids, and dianhydrides substituted 1,1,1-triaryl 2,2,2-trifluoroethanes which comprises: (1) 1,1-bis (dialkylaryl) 1-aryl 2,2,2-trifluoroethane, (2) 1,1-bis (dicarboxyaryl) 1-aryl 2,2,2-trifluoroethane, or (3) cyclic dianhydride or diamine of 1,1-bis (dialkylaryl) 1-aryl 2,2,2-trifluoroethanes. The synthesis of (1) is accomplished by the condensation reaction of an aryltrifluoromethyl ketone with a dialkylaryl compound. The synthesis of (2) is accomplished by the oxidation of (1). The synthesis dianhydride of (3) is accomplished by the conversion of (2) to its corresponding cyclic dianhydride. The synthesis of the diamine is accomplished by the similar reaction of an aryltrifluoromethyl ketone with aniline or aklyl substituted or disubstituted anilines. Also, other derivatives of the above are formed by nucleophilic displacement reactions.

Alston, William B.↗

Substituted 1,1,1-triaryl 2,2,2-trifluoroethanes and processes for their synthesis

Synthetic procedures to tetraalkyls, tetraacids, and dianhydrides substituted 1,1,1-triaryl 2,2,2-trifluoroethanes which comprises: (1) 1,1-bis(dialkylaryl) 1-aryl-2,2,2-trifluoroethane, (2) 1,1-bis(dicarboxyaryl) 1-aryl-2,2,2-trifluoroethane, or (3) cyclic dianhydride or diamine of 1,1-bis(dialkylaryl) 1-aryl-2,2,2-trifluoroethanes. The synthesis of (1) is accomplished by the condensation reaction of an aryltrifluoromethyl ketone with a dialkylaryl compound. The synthesis of (2) is accomplished by oxidation of (1). The synthesis dianhydride of (3) is accomplished by the conversion of (2) to its corresponding cyclic dianhydride. The synthesis of the diamine is accomplished by the similar reaction of an aryltrifluoromethyl ketone with aniline or alkyl substituted or disubstituted anilines. Also, other derivatives of the above are formed by nucleophilic displacement reactions.

Alston, William B.↗

Di(hydroxyphenyl)- 1,2,4-triazole monomers

The di(hydroxyphenyl)- 1,2,4-triazole monomers were first synthesized by reacting bis (4-hydroxyphenyl) hydrazide with aniline hydrochloride at 250 C in the melt and also by reacting 1,3 or 1,4-bis- (4-hydroxyphenyl)- phenylene- dihydrazide with 2 moles of aniline hydrochloride in the melt. Purification of the di(hydroxyphenyl)- 1,2,4-triazole monomers was accomplished by recrystallization. Poly (1,2,4-triazoles) (PT) were prepared by the aromatic nucleophilic displacement reaction of di(hydroxyphenyl)- 1,2,4-triazole monomers with activated aromatic dihalides or activated aromatic dinitro compounds. The reactions were carried out in polar aprotic solvents such as sulfolane or diphenylsulfone using alkali metal bases such as potassium carbonate at elevated temperatures under nitrogen. This synthetic route has provided high molecular weight PT of new chemical structure, is economically and synthetically more favorable than other routes, and allows for facile chemical structure variation due to the availability of a large variety of activated aromatic dihalides.

Connell, John W.↗

Substituted 1,1,1-triaryl-2,2,2-trifluoroethanes and processes for their synthesis

Synthetic procedures are given for tetraalkyl, tetraacid and dianhydrides substituted 1,1,1-triaryl-2,2,2-trifluoroethanes which comprises: (1) 1,1-bis (dialkylaryl) 1-aryl-2,2,2 trifluoroethane; (2) 1,1-bis (dicarboxyaryl) 1-aryl-2,2,2 trifluoroethane; or (3) cyclic dianhydride or diamine of 1,1-bis (dialkylaryl) 1-aryl-2,2,2 trifluoroethanes. The synthesis of (1) is accomplished by the condensation reaction of an aryltrifluoromethyl ketone with a dialkylaryl compound. The synthesis of (2) is accomplished by oxidation of (1). The synthesis dianhydride of (3) is accomplished by the conversion of (2) to its corresponding cyclic dianhydride. The synthesis of the diamine is accomplished by the similar reaction of an aryltrifluoromethyl ketone with aniline or alkyl substituted or disubstituted anilines. Also, other derivatives of the above are formed by nucleophilic displacement reactions.

Alston, William B.↗

Three-Dimensional Polybenzobisoxazoles and Polybenzobisthiazoles

Due to the poor compressive strength properties of high performance liquid crystalline polymers such as polybenzobisoxazoles (PBOs) and polybenzobisthiazoles (PBTs), we have prepared homopolymers and copolymers with PBO and PBT pendant groups on a central star-like unit, 2.7-diamino-9,9'-bis(4-aminophenyl)fluorene, in order to improve upon their compressive strength properties. The fluorene moiety was prepared by the reaction of 2,7-dinitro-9-fluorene with aniline and aniline hydrochloride, followed by reduction with palladium on carbon. The central star-like unit was characterized by FTIR, FTNMR, and elemental analysis. The PBO and PBT pendant groups were synthesized by the polycondensation of 4,6-diaminoresorcinol dihydrochloride with terephthaloyl chloride and 2,5-diamino-1,4-benzendithiol dihydrochloride with terephthaloyl chloride in poly(phosphoric acid), respectively. The resulting linear polymers containing the dicarboxylic end groups were attached to the central star-like unit by refluxing with 2,7-diamino-9,9'-bis(4-aminophenyl) fluorene to give the star-like polymers. The star-like PBO and PBT were soluble in methanesulfonic acid. Further characterization of the polymers is ongoing.

Bray, M.↗

Shadowgraph Study of Gradient Driven Fluctuations

A fluid or fluid mixture, subjected to a vertical temperature and/or concentration gradient in a gravitational field, exhibits greatly enhanced light scattering at small angles. This effect is caused by coupling between the vertical velocity fluctuations due to thermal energy and the vertically varying refractive index. Physically, small upward or downward moving regions will be displaced into fluid having a refractive index different from that of the moving region, thus giving rise to the enhanced scattering. The scattered intensity is predicted to vary with scattering wave vector q, as q(sup -4), for sufficiently large q, but the divergence is quenched by gravity at small q. In the absence of gravity, the long wavelength fluctuations responsible for the enhanced scattering are predicted to grow until limited by the sample dimensions. It is thus of interest to measure the mean-squared amplitude of such fluctuations in the microgravity environment for comparison with existing theory and ground based measurements. The relevant wave vectors are extremely small, making traditional low-angle light scattering difficult or impossible because of stray elastically scattered light generated by optical surfaces. An alternative technique is offered by the shadowgraph method, which is normally used to visualize fluid flows, but which can also serve as a quantitative tool to measure fluctuations. A somewhat novel shadowgraph apparatus and the necessary data analysis methods will be described. The apparatus uses a spatially coherent, but temporally incoherent, light source consisting of a super-luminescent diode coupled to a single-mode optical fiber in order to achieve extremely high spatial resolution, while avoiding effects caused by interference of light reflected from the various optical surfaces that are present when using laser sources. Results obtained for a critical mixture of aniline and cyclohexane subjected to a vertical temperature gradient will be presented. The sample was confined between two horizontal parallel sapphire plates with a vertical spacing of 1 mm. The temperatures of the sapphire plates were controlled by independent circulating water loops that used Peltier devices to add or remove heat from the room air as required. For a mixture with a temperature gradient, two effects are involved in generating the vertical refractive index gradient, namely thermal expansion and the Soret effect, which generates a concentration gradient in response to the applied temperature gradient. For the aniline/cyclohexane system, the denser component (aniline) migrates toward the colder surface. Consequently, when heating from above, both effects result in the sample density decreasing with altitude and are stabilizing in the sense that no convective motion occurs regardless of the magnitude of the applied temperature gradient. The Soret effect is strong near a binary liquid critical point, and thus the dominant effect is due to the induced concentration gradient. The results clearly show the divergence at low q and the predicted gravitational quenching. Results obtained for different applied temperature gradients at varying temperature differences from the critical temperature, clearly demonstrate the predicted divergence of the thermal diffusion ratio. Thus, the more closely the critical point is approached, the smaller becomes the temperature gradient required to generate the same signal. Two different methods have been used to generate pure concentration gradients. In the first, a sample cell was filled with a single fluid, ethylene glycol, and a denser miscible fluid, water, was added from below thus establishing a sharp interface to begin the experiment. As time went on the two fluids diffused into each other, and large amplitude fluctuations were clearly observed at low q. The effects of gravitational quenching were also evident. In the second method, the aniline/cyclohexane sample was used, and after applying a vertical temperature gradient for several hours, the top and bottom temperatures were set equal and the thermal gradient died on a time scale of seconds, leaving the Soret induced concentration gradient in place. Again, large-scale fluctuations were observed and died away slowly in amplitude as diffusion destroyed the initial concentration gradient.

Cannell, David↗

Ignition Delay Experiments with Small-scale Rocket Engine at Simulated Altitude Conditions Using Various Fuels with Nitric Acid Oxidants / Dezso J. Ladanyi

Ignition delay determinations of several fuels with nitric oxidants were made at simulated altitude conditions utilizing a small-scale rocket engine of approximately 50 pounds thrust. Included in the fuels were aniline, hydrazine hydrate, furfuryl alcohol, furfuryl mercaptan, turpentine, and mixtures of triethylamine with mixed xylidines and diallyaniline. Red fuming, white fuming, and anhydrous nitric acids were used with and without additives. A diallylaniline - triethylamine mixture and a red fuming nitric acid analyzing 3.5 percent water and 16 percent NO2 by weight was found to have a wide temperature-pressure ignition range, yielding average delays from 13 milliseconds at 110 degrees F to 55 milliseconds at -95 degrees F regardless of the initial ambient pressure that ranged from sea-level pressure altitude of 94,000 feet.

XYLIDINE↗