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At least 1,099 records · Page 61

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NASA NTRS1986

Shock-tube pyrolysis of acetylene - Sensitivity analysis of the reaction mechanism for soot formation

The impact of thermodynamic parameters on the sensitivity of model predictions of soot formation by shock-tube pyrolysis of acetylene were assessed analytically. The pyrolysis process was treated as having three components: initiation, the initial pyrolysis stages; cyclization, formation of larger molecules and radicals and small aromatic molecules; and polymerization, further growth of aromatic rings. Rate equations are reviewed for each component. Thermodynamic effects were assessed by varying the C2H-H and C2H3-H bond energies and the Ct-(Ct) group additivity value. Any change in the C2H-H bond energy had a significant impact on the temperature and the maximum amount of the soot yield. The findings underscore the necessity of using accurate thermodynamic data for modeling high-temperature chemical kinetics.

Frenklach, M.↗

NASA NTRS1989

Bis(4-(3,4-dimethylenepyrrolidyl)-phenyl) methane

It is the primary object of the present invention to prepare high temperature polymeric materials, especially linear aromatic polyimides, which maintain their integrity and toughness during long exposure times at elevated temperatures. According to the present invention, this object is achieved, and the attending benefits are obtained, by first providing the bis(exocyclodiene) bis(4-(3,4-dinethylene pyrrolidyl) phenyl) methane, which is formed from the monomer N-phenyl 3,4-dimethylene pyrrolidine. This bis-(exocyclodiene) undergoes Diels-Alder reaction with a bismaleimide without the evolution of gaseous by-products, to form the aromatic polyimide.

Ottenbrite, Raphael M.↗

NASA NTRS1989

Fracture toughness of polyimide films

Two aromatic polyimides and an aromatic polyamide-imide were tested in single edge notched tension. Fracture toughnesses, normalized to 25 micron film thickness ranged from 1.65 to 5.4 MPa m sup 1/2. LARC-TPI, a thermoplastic polyimide, showed evidence of crazing ahead of a growing crack whereas the other materials formed a shear yielded zone.

Hinkley, J. A.↗

NASA NTRS1990

Chemistry and properties of new poly(arylene ether imidazoles)

As part of a program to develop high-temperature high-performance structural resins for aerospace applications, the chemistry and properties of new poly(arylene ether imidazoles) were investigated. The polymers were prepared by the nucleophilic displacement reaction of aromatic bis(imidazolephenols) with activated aromatic difluoro compounds. The amorphous thermoplastic polymers exhibited glass transition temperatures from 230 to 301 C, inherent viscosities from 0.46 to 1.46 dL/g, and number-average molecular weights as high as 59,300 g/mole. The polymers exhibit good toughness, adhesive, composite, and film properties. The chemical, physical, and mechanical properties of these materials are discussed.

Connell, J. W.↗

NASA NTRS1990

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.↗

NASA NTRS1990

Evaluation of two bisimide additives in LARC-TPI adhesive

The processability of aromatic polyimides can be improved by the addition of bis (amide) acids or bisimides to LARC-TPI. These low molecular weight additives apparently lower the melt viscosity of aromatic polyimides without affecting the glass transition temperature. Well-consolidated, fiber reinforced composites were fabricated using this technology. LARC-TPI can be processed as a thermoplastic polyimide to form high strength bonds, however, this is generally accomplished by processing at relatively high bonding pressures. An adhesive investigation is presented on the effects of two bisimide additives to LARC-TPI in an attempt to improve the bonding process by lowering the viscosity of the material to achieve improved bond strength properties. Apparently, the high flow which is exhibited by the additives when they melt, tended to be masked by the more viscous LARC-TPI.

Progar, Donald J.↗

NASA NTRS1990

Bis (4-(3,4-dimethylene-pyrrolidyl)-phenyl) methane

The primary objective is to prepare high temperature polymeric materials, especially linear aromatic polyimides, which maintain their integrity and toughness during long exposure times at elevated temperatures. The attained benefits are obtained by first providing the bis (exocyclodiene) bis (4-(3,4-dimethylene-pyrrolidyl)-phenyl) methane, which is a novel material formed from the monomer N-phenyl-3,4-dimethylene-pyrrolidine. This compound undergoes Diels-Alder reaction with a bismaleimide, without the evolution of gaseous by-products, to form the aromatic polyimide bis (4-(3,4-dimethylene-pyrrolidyl)-phenyl) methane.

Ottenbrite, Raphael M.↗

NASA NTRS1989

Red fluorescence and 3-12 micron emission in NGC 2023, HD 44179, M 82, and Lynds 1780

A red excess observed in the Red Rectangle (HD 44179), was attributed to a possible molecular fluorescence mechanism was discovered in NGC 2023 and analyzed in subsequent work in this and other nebulae. An unexpected red light excess was also noticed in a high latitude dark cloud L 1780. The fluorescence was attributed to hydrogenated amorphous carbon by Duley (1985), on the basis of laboratory work. Alternatively, transitions between electronic states of free polycyclic aromatic hydrocarbon molecules, by-passing the cascade along the vibrational states was considered. In L 1780, the red excess was related to the 12 micron emission detected by IRAS. A quantitative comparison of the intensity of the red fluorescence and that of the 3 to 12 micron features is thus warranted in helping assess the physical properties of large interstellar molecules. The red fluorescence radiation, F(R), appears as a bump on the spectra between 0.6 and 0.9 micron. Values were deduced from the spectra for HD 44179, and for the high latitude cloud L 1780. Corrections for the extinction, both interstellar and internal to the nebulae, were included. The 3 to 12 micron brightness, F(IR), was obtained through integration of the spectra for NGC 2023, and for HD 44179 after removal of a smooth continuum due to hot large grains. The values of the ratio of fluorescence flux to the infrared flux, F(R)/F(IR), are summarized. Red fluorescence and infrared radiation are two separate ways to access to the size of the molecules through observation, and it is rewarding that both approaches give similar results. These findings bring a striking coherence into the physical description of the particles, and add further support to the initial attribution of the infrared features to polycyclic aromatic hydrocarbons (PAHs).

Ryter, Charles↗

NASA NTRS1991

Photoabsorption and photodissociation of molecules important in the interstellar medium

The photoabsorption, photodissociation, and fluorescence cross sections of interstellar molecules are measured at 90 to 250 nm. These quantitative optical data are needed for the understanding of the formation and destruction processes of molecules under the intense interstellar UV radiation field. Research covering the following topics is presented: (1) fluorescences from photoexcitation of CH4, CH3OH, and CH3SH; (2) NO gamma emission from photoexcitation of NO; (3) photoexcitation cross sections of aromatic molecules; (4) IR emission from UV excitation of HONO2; (5) IR emission from UV excitation of benzene and methyl-derivitives; and (6) IR emission from UV excitation of polycyclic aromatic hydrocarbon molecules.

Lee, Long C.↗

NASA NTRS1990

Hydrocarbon emission features in the IR spectra of warm supergiants

Observations in the 3-13 micron range are presented for two objects possessing the unidentified 21-micron feature, IRAS 22272 and IRAS 07134, which were obtained in the course of search for circumstellar aromatic hydrocarbon (PAH) emission bands. The 3.3 and 6.2 micron bands are attributed to circumstellar PAH molecules, and the 6-9 micron plateau and the 12- and 6.9-micron lines are attributed to larger, aromatic hydrocarbon clusters. These are the coolest stars known to exhibit the IR emission bands. The 21-micron feature is conjectured to also originate in a carbonaceous carrier.

Buss, R. H., Jr.↗

NASA NTRS1991

High-resolution spectra of the 3.29 micron interstellar emission feature - A summary

High spectral resolution observations of the 3.29-micron interstellar emission feature show two types of profiles. Type 1 has a central wavelength of 3.289-micron and is observed in extended objects such as planetary nebulae and H II regions. Type 2 has a central wavelength of 3.296 microns and is observed around a small number of stellar sources. Type 2 has a full width at half-maximum of 0.020 micron; Type 1 has a broader FWHM, perhaps as much as 0.042 micron, but this is uncertain because of contamination by Pf(delta) emission. These profiles are tabulated for comparison to laboratory data. It is found that no proposed identification for the 3.29-micron emission feature definitely matches the observational spectra, although amorphous aromatic materials and heated polycyclic aromatic hydrocarbons tend to fit the best.

Tokunaga, A. T.↗

NASA NTRS1991

A process for preparing an assembly of an article and a polyimide which resists dimensional change, delamination, and debonding when exposed to changes in temperature

An assembly of an article and a polyimide composition is prepared. The assembly resists dimensional change, delamination, or debonding when exposed to changes to temperature. An article is provided. A polyamic acid solution which yields a polyimide having a low coefficient of thermal expansion (CTE) was prepared. Equimolar quantities of an aromatic diamine and an aromatic dianhydride were reacted in a solvent medium to form a polyamic acid solution. A metal ion containing additive was added to the solution. Examples of this additive are: TbCl3, DyCl3, ErCl3, TmCl3, Al(C5H7O2)3, and Er2S3. The polyamic acid solution was imidized and is combined with the article to form the assembly.

Stoakley, Diane M.↗

NASA NTRS1992

Tough, high performance, addition-type thermoplastic polymers

A tough, high performance polyimide is provided by reacting a triple bond conjugated with an aromatic ring in a bisethynyl compound with the active double bond in a compound containing a double bond activated toward the formation of a Diels-Adler type adduct, especially a bismaleimide, a biscitraconimide, or a benzoquinone, or mixtures thereof. Addition curing of this product produces a high linear polymeric structure and heat treating the highly linear polymeric structure produces a thermally stable aromatic addition-type thermoplastic polyimide, which finds utility in the preparation of molding compounds, adhesive compositions, and polymer matrix composites.

Pater, Ruth H.↗

NASA NTRS1992

Cyclopentadiene evolution during pyrolysis-gas chromatography of PMR polyimides

The effect of formulated molecular weight (FMW), extent of cure, and cumulative aging on the amount of cyclopentadiene (CPD) evolved from Polymerization of Monomeric Reactants (PMR) polyimides were investigated by pyrolysis-gas chromotography (PY-GC). The PMR polyimides are additional crosslinked resins formed from an aromatic diamine, a diester of an aromatic tetracarboxylic acid and a monoester of 5-norbornene-2, 3-dicarboxylic acid. The PY-GC results were related to the degree of crosslinking and to the thermo-oxidative stability (weight loss) of PMR polyimides. Thus, PY-GC has shown to be a valid technique for the characterization of PMR polyimide resins and composites via correlation of the CPD evolved versus the thermal history of the PMR sample.

Alston, William B.↗

NASA NTRS1991

Evaluation of optically transparent polyetherimide films for applications in space

Several series of aromatic polyetherimide films have been synthesized and characterized with the objective of obtaining maximum optical transparency for applications in space. Incorporation of phenoxy groups into aromatic polyimides has resulted in a reduction in the color intensity of these films compared to commercial polyimide film by reducing electronic interactions between polymer chains. The resulting lightly colored to colorless polyetherimide films have been characterized by UV-visible and infrared spectroscopy before and after exposure to varying doses of UV and electron irradiation designed to simulate use as second-surface mirror thermal control coatings. After exposure to 300 equivalent solar hours UV irradiation and 1 MeV electron irradiation, the polyetherimides were 2.2 to 2.6 times more transparent than commercial polyimide film of the same thickness.

St. Clair, Anne K.↗

NASA NTRS1992

New Synthesis Of Poly(1,3,4-Oxadiazoles)

Synthesis via aromatic nucleophilic displacement yields new high-molecular-weight polymers. Polymers exhibited good mechanical and thermal properties. Synthetic route provided high-molecular-weight POX of new chemical structure, potentially more economical. Availability of large variety of activated aromatic dihalides, facilitates variation of chemical structures. Exhibit properties making them useful as films. Also useful in coatings, adhesives, moldings, and composites.

Connell, John W.↗

NASA NTRS1993

Simplified jet-A kinetic mechanism for combustor application

Successful modeling of combustion and emissions in gas turbine engine combustors requires an adequate description of the reaction mechanism. For hydrocarbon oxidation, detailed mechanisms are only available for the simplest types of hydrocarbons such as methane, ethane, acetylene, and propane. These detailed mechanisms contain a large number of chemical species participating simultaneously in many elementary kinetic steps. Current computational fluid dynamic (CFD) models must include fuel vaporization, fuel-air mixing, chemical reactions, and complicated boundary geometries. To simulate these conditions a very sophisticated computer model is required, which requires large computer memory capacity and long run times. Therefore, gas turbine combustion modeling has frequently been simplified by using global reaction mechanisms, which can predict only the quantities of interest: heat release rates, flame temperature, and emissions. Jet fuels are wide-boiling-range hydrocarbons with ranges extending through those of gasoline and kerosene. These fuels are chemically complex, often containing more than 300 components. Jet fuel typically can be characterized as containing 70 vol pct paraffin compounds and 25 vol pct aromatic compounds. A five-step Jet-A fuel mechanism which involves pyrolysis and subsequent oxidation of paraffin and aromatic compounds is presented here. This mechanism is verified by comparing with Jet-A fuel ignition delay time experimental data, and species concentrations obtained from flametube experiments. This five-step mechanism appears to be better than the current one- and two-step mechanisms.

Lee, Chi-Ming↗

NASA NTRS1993

Polyimides containing pendent trifluoromethyl groups

Several new polyimides containing trifluoromethyl groups were prepared from the reaction of various aromatic dianhydrides and two new diamines containing trifluoromethyl groups, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)biphenyl and l,4-bis(3-amino-5-trifluoromethylphenoxy)benzene. The diamines were prepared from the aromatic nucleophilic displacement of the disodium salts of 4,4'-biphenol or hydroquinone with 3,5-dinitrobenzotrifluoride followed by hydrogenation of the resultant dinitro compounds. The thermally cured polyimides exhibited glass transition temperatures between 186 and 262 C. By thermogravimetric analysis, the polyimides exhibited 5 percent weight losses at 484-527 C in nitrogen and 452-506 C in air.

Havens, S. J.↗