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At least 181 records · Page 10
All sourcesNASA NTRSDOE OSTI
NASA NTRS1982

Oxidation and formation of deposit precursors in hydrocarbon fuels

A practical fuel, home heating oil no. 2 (Fuel C), and the pure hydrocarbon, n-dodecane, were subjected to mild oxidation at 130 C and the resulting oxygenated reaction products, deposit precursors, were analyzed using field ionization mass spectrometry. Results for fuel C indicated that, as oxidation was initially extended, certain oxygenated reaction products of increasing molecular weights in the form of monomers, dimers and some trimers were produced. Further oxidation time increase resulted in further increase in monomers but a marked decrease in dimers and trimers. This suggests that these larger molecular weight products have proceeded to form deposit and separated from the fuel mixture. Results for a dodecane indicated that yields for dimers and trimers were very low. Dimers were produced as a result of interaction between oxygenated products with each other rather than with another fuel molecule. This occurred even though fuel molecule concentration was 50 times, or more greater than that for these oxygenated reaction products.

Buttrill, S. E., Jr.↗
NASA NTRS1983

Fluorescence from polystyrene - Photochemical processes in polymeric systems, 7

Results are presented for measurements of the fluorescence spectra of polystyrene in dilute solution and in pure solid films. It is determined that a major potential source of experimental error is the concurrent photooxidative degradation in air which may obscure fluorescence emission from monomeric sites in solid films at 25 C. The fluorescence spectra of oriented films are evaluated in terms of the monomer to excimer fluorescence intensity ratio and the excimer 'red shift'. The monomer to excimer fluorescence intensity ratio is determined to be significantly higher in fluid solution than in solid film.

Gupta, M. C.↗
NASA NTRS1984

Self-deactivation of water vapor - Role of the dimer

A phenomenological multiple-relaxation theory of the deactivation rate constant for the nu-2 (1 - 0) bending mode of water vapor is presented which incorporates the role not only of the excited monomer but also of the bound molecular complex, in particular the dimer. The deactivation takes place by means of three parallel processes: (1) collisional deexcitation of the excited monomer, (2) a two-step reaction involving association and spontaneous redissociation of an H2O collision complex, and (3) spontaneous dissociation of the stably bound H2O dimer. Oxygen, but not nitrogen or argon, serves as an effective chaperon for the formation of the activated complex. This observation explains the impurity dependence of the self-deactivation rate constant of water vapor. Analysis of an ultrasonic absorption peak based on the third process yields values for the standard entropy and enthalpy of dissociation of the stably bound H2O dimer.

Zuckerwar, A. J.↗
NASA NTRS1985

Graphite/PMR polyimide composites with improved toughness

The toughness of composites made with modified PMR (polymerization of monomer reactants) polyimides and Celion 6000 graphite fibers was studied. Various types/levels of monomer reactants containing flexible links were incorporated into PMR resin compositions used to prepare composites. The composites were evaluated for toughness using instrumented drop weight and 10 deg off axis tensile tests at room temperature, and for strength using flexure and short beam shear tests at room temperature and at elevated temperature. The effect of resin composition on composite processability, thermo-oxidative stability, toughness and mechanical properties are discussed.

Vannucci, R. D.↗
NASA NTRS1985

Search for the Universal Ancestors

By its nature, the study of the origins of life is multidisciplinary, requiring contributions from astronomers, biologists, chemists, geologists, physicists, and many others. Partial answers are provided to many questions about organic chemical evolution and the origin of life. It is observed that the gaps in our knowledge concerning the steps from the nonliving to the living are numerous. Among these gaps are: (1) a solar system formation with its accumulation of raw materials; (2) the synthesis of the life forming monomers, such as the amino acids, nucleotides, and lipids; (3) the condensation of these monomers into useful polymers, such as proteins and nucleic acids; (4) the sequestering of these materials into droplets of proteinoid or membrane-like structures; and (5) the development of a chemical memory (the genetic code) to pass on to the progeny the information acquired.

Hartman, H.↗
NASA NTRS1984

PMR polyimide composites for aerospace applications

A novel class of addition-type polyimides has been developed in response to the need for high temperature polymers with improved processability. The new plastic materials are known as PMR (for in situ polymerization of monomer reactants) polyimides. The highly processable PMR polyimides have made it possible to realize much of the potential of high temperature resistant polymers. Monomer reactant combinations for several PMR polyimides have been identified. The present investigation is concerned with a review of the current status of PMR polyimides. Attention is given to details of PMR polyimide chemistry, the processing of composites and their properties, and aerospace applications of PMR-15 polyimide composites.

Serafini, T. T.↗
NASA NTRS1985

Optically transparent/colorless polyimides

Several series of linear aromatic polyimide films have been synthesized and characterized with the objective of obtaining maximum optical transparency. Two approaches have been used as part of this structure-property relationship study. The first approach is to vary the molecular structure so as to separate chromophoric centers and reduce electronic interactions between polymer chains to lower the intensity of color in the resulting polymer films. A second and concurrent approach is to perform polymerizations with highly purified monomers. Glass transition temperatures of thermally cured polyimide films are obtained by thermomechanical analysis and thermal decomposition temperatures are determined by thermogravimetric analysis. Transmittance UV-visible spectra of the polyimide films are compared to that of a commercial polyimide film. Fully imidized films are tested for solubility in common organic solvents. The more transparent films prepared in this study are evaluated for use on second-surface mirror thermal control coating systems. Lightly colored to colorless films are characterized by UV-visible spectroscopy before and after exposure to 300 equivalent solar hours UV irradiation and varying doses of 1 MeV electron irradiation. The effects of monomer purity, casting solvent and cure atmosphere on polyimide film transparency are also investigated.

Stclair, A. K.↗
NASA NTRS1985

High temperature resistant polyimide from tetra ester, diamine, diester and N-arylnadimide

The invention described relates to improved polyimide resins which are noted for their high thermal and oxidative stability, high strength at elevated temperatures and which exhibit many other outstanding physical and chemical properties, especially useful in high temperature applications. The polyimides are prepared by the reaction, with application of heat of a mixture of monomers comprising: (1) a dialkyl or tetraalkyl ester of an aromatic tetracarboxylic acid, (2) and aromatic diamine, (3) a monoalkyl or dialky ester of a dicarboxylic acid, and (4) a N-arylnadimide such as N-phenylnadimide. Polyimides of monomers (1), (2) and (3) are known.

Pater, R. H.↗
NASA NTRS1985

Graphite/PMR polyimide composites with improved toughness

The toughness of composites made with modified PMR (Polymerization of monomer reactants) polyimides and Celion 6000 graphite fibers was studied. Various types/levels of monomer reactants containing flexible links were incorporated into PMR resin compositions used to prepare composites. The composites were evaluated for toughness using instrumented drop weight and 10 deg off axis tensile tests at room temperature, and for strength using flexure and short beam shear tests at room temperature and at elevated temperature. The effect of resin composition on composite processability, thermo-oxidative stability, toughness and mechanical properties are discussed.

Vannucci, R. D.↗
NASA NTRS1987

Fire- and Heat-Resistant Laminating Resins

Imide compounds containing phosphourus thermally polymerized. New maleimido- or citraconimido-end-capped monomers, have relatively low melting temperatures, polymerized at moderate temperatures to rigid bisimide resins without elimination of volatiles. Monomers dissolve in such solvents as methyl ethyl ketone, acetone, and tetrahydrofuran, suitable and perferred as "varnish solvents" for composite fabrication. Low melting points of these componds allow use as adhesives without addition of solvents.

Kourtides, Demetrius A.↗
NASA NTRS1987

Fire and heat resistant laminating resins based on malemeido and citraconimido substituted 1 -2,4- and -2,6- diaminobenzenes

A novel class of fire and heat resistant bisimide resins prepared by thermal polymerization of maleimido or citraconimido substituted 1-(dialkox phosphonyl) methyl-2-4 and -2,6-diamino benzenes was presented. The polymer precursors are prepared by reacting 1-(diorgano oxyphosphonyl) methyl-2-4- and -2,6-diamino benzenes with maliec anhydride or citraconic anhydride in a mole ratio 1:2. Chain extension of the monomers is achieved by reacting the mono-N-maleimido derivaties of 1 (diorgano oxyphosphonyl) methyl -2,4- and -2,6-diamino benzenes with aryl tetracarboxylic dianhydrides, such as benzophenone tetracarboxylic dianhydride, or aryl diisocyanates, such as methylene bis(4-phenyl isocyanate), in a mole ratio 2:1. The polymerization of the monomers is studied by diferential scanning calorimetry and the thermal stability of the polymers is ascertained by thermogravimetric analysis.

Mikroyannidis, John A.↗
NASA NTRS1987

Fire and heat resistant laminating resins based on maleimido and citraconimido substituted 1-(diorgano oxyphosphonyl) methyl -2,4- and -2,6- diaminobenzenes

A class of fire and heat resistant bisimide resins prepared by thermal polymerization of maleimido or citraconimido substituted 1-((dialkoxyphosphonyl) methyl)-2-4 and -2,6-diaminobenzenes are described. The polymer precursors are prepared by reacting 1-((diorganooxyphosphonyl) methyl)-2-4 and -2,6-diaminobenzenes with maleic anhydride or citraconic anhydride in a mole ratio 1:2. Chain extension of the monomers is achieved by reacting the mono-N-maleimido derivatives of 1-((diorganooxyphosphonyl) methyl)-2,4 and -2,6-diaminobenzenes with aryl tetracarboxylic dianhydrides, such as benzophenone tetracarbocylic dianhydride, or aryl diisocyanates, such as methylenebis (4-phenylisocyanate), in a mole ratio 2:1. The polymerization of the monomers is studied by differential scanning calorimetry (DSC) and the thermal stability of the polymers is ascertained by thermogravimetric analysis (TGA).

Mikroyannidis, John A.↗
NASA NTRS1986

Electronic energy transfer and quenching in copolymers of styrene and 2-(2-prime-hydroxy -5-prime-vinylphenyl)-2H-benzotriazole Photochemical processes in polymeric systems. X

Intensity and lifetime quenching of the polystyrene monomer and excimer fluorescence emission by a pendant quencher have been studied in the solid state and in solution for a series of copolymers of styrene and 2-(2-prime-hydroxy-5-prime-vinylphenyl)-2H-benzotriazole. Two mechanisms of quenching have been identified. One involves interception of the migrating monomer excitation by the quencher, and the other involves a single-step Foerster energy-transfer process from the excimer traps to a quencher. The relative efficiencies of these two quenching mechanisms in the solid state and in solution have been compared and related to the efficiency of electronic energy migration. An estimate of the excimer trap concentration in solid polystyrene is also reported.

Coulter, D. R.↗
NASA NTRS1987

Ketimine modifications as a route to novel amorphous and derived semicrystalline poly(arylene ether ketone) homo- and copolymers

A series of amine terminal amorphous poly(arylene ether ketone) oligomers of controlled molecular weights (2-15 K) were synthesized. These oligomers have been found to undergo 'self-crosslinking' reactions upon heating above 220 C, via the reaction of the terminal amine groups with the in-chain keto carbonyl functionalities. The resulting networks are ductile, chemically resistant, and nonporous. The networks obtained via generated ketimine functionality were characterized by solid state NMR. They have also been found to be remarkably stable toward hydrolysis. Ketimine functional bishalide monomers have also been synthesized. Such monomers have been utilized to synthesize a wide variety of amorphous poly(arylene ether) ketimine polymers. A high molecular weight hydroquinone functional poly(arylene ether) ketimine has been acid treated to regenerate a poly(arylene ether ketone) backbone in solution. This novel procedure thus allows for the synthesis of important matrix resins under relatively mild conditions.

Mohanty, D. K.↗
NASA NTRS1988

Polyphenylquinoxalines via Aromatic Nucleophilic Displacement

Polyphenylquinoxalines are produced by an aromatic nucleophilic displacement reaction involving an activated aromatic dihalide with an appropriate quinoxaline monomer. Polyphenylquinoxalines are high temperature thermoplastics used as adhesives, coatings, films and composite matrices. The novelty of this invention is threefold: (1) some of the quinoxaline monomers are new compositions of matter; (2) the phenylquinoxaline polymers which are the end products of the invention are new compositions of matter; and (3) the method of forming the polymers is novel, replacing a more costly prior art process, which is also limited in the kinds of products prepared therefrom.

Hergenrother, Paul M.↗
NASA NTRS1988

Fire and heat resistant laminating resin based on maleimido and citraconimido substituted 1-(diorganooxyphosphonyl-methyl)-2,4- and -2,6-diaminobenzenes

The subject invention pertains to a novel class of fire-and heat-resistant bisimide resins prepared by thermal polymerization of maleimido or citraconimido substituded 1-(dialkoxyphosphonyl)-methyl-2-4 and -2,6-diaminobenzenes. Typical polymer presursors have the chemical structure wherein R is alkyl, substituted alkyl or aryl, and R sup 1 is hydrogen or lower alkyl. The polymer precursors are prepared by reacting 1-(diorganooxyphosphonyl)methyl-2-4 and -2,6-diaminobenzenes with maleic anhydride or citraconic anhydride in a mole ratio 1:2. Chains extension of the monomers is achieved by reacting the mono-N-maleimido derivatives of 1-(diorganooxyphosphonyl)methyl-2,4 and -2,6-diaminobenzenes with aryl tetracarboxylic dianhydrides, such as benzophenone tetracarboxylic diandydride, or aryl diisocyanates, such as methylenebis (4-phenylisocyanate), in a mole ratio 2:1. The polymerization of the monomers is studied by differential scanning calorimetry (DSC) and the thermal stability of the polymers is ascertained by thermogravimetric analysis (TGA).

James M Beggs↗
NASA NTRS1989

The role of cometary particle coalescence in chemical evolution

Important prebiotic organic compounds might have been transported to earth in dust or produced in vapor clouds resulting from atmospheric explosions or impacts of comets. These compounds coalesced in the upper atmosphere with particles ejected from craters formed by impacts of large objects. Coalescence during exposure to UV radiation concentrated organic monomers and enhanced formation of oligomers. Continuing coalescence added material to the growing particles and shielded prebiotic compounds from prolonged UV radiation. These particles settled into the lower atmosphere where they were scavenged by rain. Aqueous chemistry and evaporation of raindrops containing monomers in high temperature regions near the earth's surface also promoted continued formation of oligomers. Finally, these oligomers were deposited in the oceans where continued prebiotic evolution led to the most primitive cell. Results of present studies suggest that prebiotic chemical evolution may be an inevitable consequence of impacting comets during the late accretion of planets anywhere in the universe if oceans remained on those planetary surfaces.

Oberbeck, V. R.↗
NASA NTRS1992

Poly(1,3,4-oxadiazoles) via aromatic nucleophilic displacement

Poly(1,3,4-oxadiazoles) (POX) are prepared by the aromatic nucleophilic displacement reaction of di(hydroxyphenyl) 1,3,4-oxadiazole monomers with activated aromatic dihalides or activated aromatic dinitro compounds. The polymerizations are carried out in polar aprotic solvents such as sulfolane or diphenylsulfone using alkali metal bases such as potassium carbonate at elevated temperatures under nitrogen. The di(hydroxyphenyl) 1,3,4-oxadiazole monomers are synthesized by reacting 4-hydroxybenzoic hydrazide with phenyl 4-hydrobenzoate in the melt and also by reacting aromatic dihydrazides with two moles of phenyl 4-hydroxybenzoate in the melt. This synthetic route has provided high molecular weight POX of new chemical structure, is economically and synthetically more favorable than other routes, and allows for facile chemical structure variation due to the large variety of activated aromatic dihalides which are available.

Connell, John W.↗