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At least 577 records · Page 32

Laboratory Spectroscopy of Large Carbon Molecules and Ions in Support of Space Missions. A New Generation of Laboratory & Space Studies

Polycyclic Aromatic Hydrocarbons (PAHs) are an important and ubiquitous component of carbon-bearing materials in space. A long-standing and major challenge for laboratory astrophysics has been to measure the spectra of large carbon molecules in laboratory environments that mimic (in a realistic way) the physical conditions that are associated with the interstellar emission and absorption regions [1]. This objective has been identified as one of the critical Laboratory Astrophysics objectives to optimize the data return from space missions [2]. An extensive laboratory program has been developed to assess the properties of PAHs in such environments and to describe how they influence the radiation and energy balance in space. We present and discuss the gas-phase electronic absorption spectra of neutral and ionized PAHs measured in the UV-Visible-NIR range in astrophysically relevant environments and discuss the implications for astrophysics [1]. The harsh physical conditions of the interstellar medium characterized by a low temperature, an absence of collisions and strong VUV radiation fields - have been simulated in the laboratory by associating a pulsed cavity ringdown spectrometer (CRDS) with a supersonic slit jet seeded with PAHs and an ionizing, penning-type, electronic discharge. We have measured for the {\it first time} the spectra of a series of neutral [3,4] and ionized [5,6] interstellar PAHs analogs in the laboratory. An effort has also been attempted to quantify the mechanisms of ion and carbon nanoparticles production in the free jet expansion and to model our simulation of the diffuse interstellar medium in the laboratory [7]. These experiments provide {\it unique} information on the spectra of free, large carbon-containing molecules and ions in the gas phase. We are now, for the first time, in the position to directly compare laboratory spectral data on free, cold, PAH ions and carbon nano-sized carbon particles with astronomical observations in the UV-NIR range (interstellar UV extinction, DIBs in the NUV-NIR range). This new phase offers tremendous opportunities for the data analysis of current and upcoming space missions geared toward the detection of large aromatic systems Le., the "new frontier space missions" (Spitzer, HST, COS, JWST, SOFIA,...).

Salama, Farid↗

Ice photochemistry as a source of amino acids and other organic molecules in meteorites, and implications for the origin of life and the search for life in the Solar System

The tons of extraterrestrial organic material that come to the Earth every day probably helped to made the Earth habitable, and possibly played a role in the origin of life. At the astrochemistry lab (http://www.astrochem.orq) we investigate the formation and distribution of organic molecules in space and consider the impact such molecules may have on the habitability of planets and the search for life in the Solar System. The organic compounds in meteorites include amino acids, aromatics of various sorts including purine and pyrimidine bases, and fatty acids that form bi-layer vesicles. The origin of many of these species remains mysterious, but in recent years we and others have performed experiments that suggest low temperature radiation chemistry could account for the presence and deuterium enrichment of many of these molecules. . I will present our laboratory experiments that show the viability of low temperature radiation chemistry as a source of organic molecules such as;amino acids (Nature, 2002, 416, 401-403), amphiphiles (Astrobiology, 2003, 2, 371, Proc. Nat. Acad. Sci. 2001, 98, 815), quinones (Science, 1999, 283, 1135) and other functionalized aromatic compounds (Meteoritics, 2001, 36, 351 ; Astrophysical Journal., 2003, 582, L25), some of which were invoked as potential biomarkers in the Alan Hills 84001 Martian meteorite. Understanding how components of proteins and DNA could form in sterile space environments is also of relevance to our search for life elsewhere in the Solar System, the great task now ahead of NASA. If we find evidence of Life elsewhere in the Solar System it will probably be in form of chemical biomarkers, quintessentially biological molecules that indicate the presence of micro-organisms. While most people think of molecules such as amino acids, and nucleo-bases as good candidate biomarkers, these molecules are produced non-biotically in space and are expected to be present on the surface of other planets even in the absence of Life. Understanding the range of non-biological organic molecules which could act as false biomarkers in space is a prerequisite for any reasonable search for Life on other worlds.

Bernstein, Max↗

Space Environmentally Durable Polyimides and Copolyimides

Polyimides displaying low color in thin films, atomic oxygen resistance, vacuum ultraviolet radiation resistance, solubility in organic solvents in the imide form, high glass transition (T(sub g)) temperatures, and high thermal stability are provided. The poly(amide acid)s, copoly(amide acid)s, polyimides and copolyimides are prepared by the reaction of stoichiometric ratios of an aromatic &anhydride with diamines which contain phenylphosphine oxide groups in polar aprotic solvents. Controlled molecular weight oligomeric (amide acid)s and imides can be prepared by offsetting the stoichiometry according to the Carothers equation using excess diamine and endcapping with aromatic anhydrides. The polyimide materials can be processed into various material forms such as thin films, fibers, foams, threads, adhesive film, coatings, dry powders, and fiber coated prepreg, and uses include thin film membranes on antennas, second-surface mirrors, thermal optical coatings, and multilayer thermal insulation (MLI) blanket materials.

Connell, John W.↗

Stellar Evolutionary Effects on the Abundance of PAHS and SN-Condensed Dust in Galaxies

Spectral aid photometric observations of nearby galaxies show a correlation between the strength of their mid-IR aromatic features and their metal abundance, and a deficiency of these features in low-metallicity galaxies. The aromatic features are most commonly attributed to emission from PAH molecules. In this paper, we suggest that the observed correlation represents a trend of PAH abundance with galactic age, reflecting the delayed injection of PAHs and carbon dust into the ISM, by AGB stars in their final, post-AGB phase of their evolution. These AGB stars are the primary sources of PAHs and carbon dust in galaxies, and recycle their ejecta back to the interstellar medium only after a few hundred million years of evolution on the main sequence. In contrast, more massive stars that explode as Type II supernovae inject their metals and dust almost instantaneously after their formation. After determining the PAH abundances in 35 nearby galaxies, we use a chemical evolution model to show that the delayed injection of carbon dust by AGB stars provides a natural explanation to the dependence of the PAH content, in galaxies with metallicity. We also show that larger dust particles giving rise to the far-IR emission follow a distinct evolutionary trend closely related to the injection of dust by massive stars into the ISM.

Dwek, Eli↗

Copolyimides prepared from ODPA, BTDA and 3,4'-ODA

A copolyimide was prepared by reacting 3,4'-oxydianiline (3,4'-ODA) with a dianhydride blend comprising, based on the total amount of the dianhydride blend, about 67 to 80 mole percent of 4,4'-oxydiphthalic anhydride (ODPA) and about 20 to 33 mole percent of 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA). The copolyimide may be endcapped with up to about 10 mole percent of a monofunctional aromatic anhydride and has unbalanced stoichiometry such that a molar deficit in the dianhydride blend is compensated with twice the molar amount of the monofunctional aromatic anhydride. The copolyimide was used to prepare composites, films and adhesives. The film and adhesive properties were significantly better than those of LaRC.TM.-IA.

Chang, Alice C.↗

Poly-phenylated diamines and their use as polycondensation monomers in the synthesis of polyamide, poly(amide-imide), and polyimide polymers

New polyphenylated polynuclear aromatic diamines, such as 1,3-bis[4-aminophenyl]-2,3,5-triphenylbenzene, a process for their manufacture and their use as polycondensation components for the manufacture of polyamide, polyamide-imide and polyimide polymers are described. The polymers obtained with the aromatic diamines according to the invention are readily soluble, rigid-rod polymers and are distinguished by outstanding modulus, tensile compression strength, energy absorption, coefficient of expansion and electrical properties.

Harris, Frank W.↗

Electrically conductive polyimides containing silver trifluoroacetylacetonate

Polyimides with enhanced electrical conductivity are produced by adding a silver ion-containing additive to the polyamic acid resin formed by the condensation of an aromatic dianhydride with an aromatic diamine. After thermal treatment the resulting polyimides had surface conductivities in the range of 1.7.times.10.sup.-3 4.5 .OMEGA..sup.-1 making them useful in low the electronics industry as flexible, electrically conductive polymeric films and coatings.

Rancourt, James D.↗

Polyimides based on 4,4'-bis (4-aminophenoxy)-2,2'or 2,2', 6,6'-substituted biphenyl

This invention relates the novel diamines, the polyimide oligomers and the polyimides derived therefrom and to the method of preparing the diamines, oligomers and the polyimides. The thermoplastic polyimides derived from the aromatic diamines of this invention are characterized as having a high glass transition temperature, good mechanical properties and improved processability in the manufacture of adhesives, electronic and composite materials for use in the automotive and aerospace industry. The distinction of the novel aromatic diamines of this invention is the 2,2',6,6'-substituted biphenyl radicals which exhibit noncoplanar conformation that enhances the solubility of the diamine as well as the processability of the polyimides, while retaining a realatively high glass transition temperature and improved mechanical properties at useful temperature ranges.

Chuang, Chun-Hua K.↗

Polyimides comprising substituted benzidines

A new class of polyimides and copolyimides made from substituted benzidines and aromatic dianhydrides and other aromatic diamines. The polyimides obtained with said diamines are distinguished by excellent thermal, excellent solubility, excellent electrical properties such as very low dielectric constants, excellent clarity and mechanical properties making the polyimides ideally suited as coating materials for microelectronic apparatii, as membranes for selective molecular or gas separation, as fibers in molecular composites, as high tensile strength, high compression strength fibers, as film castable coatings, or as fabric components.

Harris, Frank W.↗

Thermoplastic copolyimides and composites therefrom

Copolyimide compositions and methods for their preparation which are melt-processible at relative low pressures, i.e. less than 1000 psi, and are suited for laminating and molding, are described. The invention additionally encompasses copolyimide precursors, reinforced polyimide composites and laminates made from said polyimides where the composite is reinforced by fibrous materials. This is achieved by reacting at least one aromatic dianhydride where each anhydride group is located on an aromatic ring with the carbonyl units in an ortho orientation relative to one another, with at least one diamine which is capable of a transmidization reaction upon incorporation into the polyimide backbone, and with at least one other diamine which is not capable of undergoing such reaction, the diamine which is capable of undergoing the transimidization reaction being present in an amount of from about 1-50 mole percent in relation to the diamine that is not susceptable to transimidization.

Harris, Frank↗

New Infrared Emission Features and Spectral Variations in Ngc 7023

We observed the reflection nebula NGC 7023, with the Short-High module and the long-slit Short-Low and Long-Low modules of the Infrared Spectrograph on the Spitzer Space Telescope. We also present Infrared Array Camera (IRAC) and Multiband Imaging Photometer for Spitzer (MIPS) images of NGC 7023 at 3.6, 4.5, 8.0, and 24 m. We observe the aromatic emission features (AEFs) at 6.2, 7.7, 8.6, 11.3, and 12.7 m, plus a wealth of weaker features. We find new unidentified interstellar emission features at 6.7, 10.1, 15.8, 17.4, and 19.0 m. Possible identifications include aromatic hydrocarbons or nanoparticles of unknown mineralogy. We see variations in relative feature strengths, central wavelengths, and feature widths, in the AEFs and weaker emission features, depending on both distance from the star and nebular position (southeast vs. northwest).

molecules↗

Structural/Radiation-Shielding Epoxies

A development effort was directed toward formulating epoxy resins that are useful both as structural materials and as shielding against heavy-ion radiation. Hydrogen is recognized as the best element for absorbing heavy-ion radiation, and high-hydrogen-content polymers are now in use as shielding materials. However, high-hydrogen-content polymers (e.g. polyethylene) are typically not good structural materials. In contrast, aromatic polymers, which contain smaller amounts of hydrogen, often have the strength necessary for structural materials. Accordingly, the present development effort is based on the concept that an ideal structural/ heavy-ion-radiation-shielding material would be a polymer that contains sufficient hydrogen (e.g., in the form of aliphatic molecular groups) for radiation shielding and has sufficient aromatic content for structural integrity.

Connell, John W.↗

Preliminary Appraisal of Ferrocene as an Igniting Agent for JP-4 Fuel and Fuming Nitric Acid

A preliminary experimental study was made of the properties of ferrocene as a solute and as a suspension in JP-4 fuel, and of the ignition delays of ferrocene - JP-4 mixture with A.F. specification 14104 white fuming nitric acid (WFNA). The investigation covered concentrations of 4 to 10 percent by weight ferrocene, and a temperature range of -40 to 80 F. The solubility of ferrocene in JP-4 is about 5 percent at room temperature and about 1 percent (extrapolated) at -80 F. The solubility is increased somewhat by increased aromatics content. Undissolved ferrocene particles of 100 mesh and smaller settle rapidly in JP-4. Clear solutions of 4 and 5 percent ferrocene in JP-4 fuels containing 10 and 25 percent by volume aromatics, respectively, do not ignite with WFNA at room temperature. Mixtures containing 10 percent ferrocene (100- mesh and smaller undissolved particles in suspension) ignited with vigorous persistent flames at room temperature, but did not ignite at -38 F. The ignition delays at room temperature, however, were widely varied; the range from 85 milliseconds to over 1 second perhaps reflected differences in degree of sedimentation.

Miller, RIley O.↗

Method and apparatus for detecting and quantifying bacterial spores on a surface

A method and an apparatus for detecting and quantifying bacterial spores on a surface. In accordance with the method: bacterial spores are transferred from a place of origin to a test surface, the test surface comprises lanthanide ions. Aromatic molecules are released from the bacterial spores; a complex of the lanthanide ions and aromatic molecules is formed on the test surface, the complex is excited to generate a characteristic luminescence on the test surface; the luminescence on the test surface is detected and quantified.

Ponce, Adrian↗

Polyimide Aerogels with Three-Dimensional Cross-Linked Structure

Polyimide aerogels with three-dimensional cross-linked structure are made using linear oligomeric segments of polyimide, and linked with one of the following into a 3D structure: trifunctional aliphatic or aromatic amines, latent reactive end caps such as nadic anhydride or phenylethynylphenyl amine, and silica or silsesquioxane cage structures decorated with amine. Drying the gels supercritically maintains the solid structure of the gel, creating a polyimide aerogel with improved mechanical properties over linear polyimide aerogels. Lightweight, low-density structures are desired for acoustic and thermal insulation for aerospace structures, habitats, astronaut equipment, and aeronautic applications. Aerogels are a unique material for providing such properties because of their extremely low density and small pore sizes. However, plain silica aerogels are brittle. Reinforcing the aerogel structure with a polymer (X-Aerogel) provides vast improvements in strength while maintaining low density and pore structure. However, degradation of polymers used in cross-linking tends to limit use temperatures to below 150 C. Organic aerogels made from linear polyimide have been demonstrated, but gels shrink substantially during supercritical fluid extraction and may have lower use temperature due to lower glass transition temperatures. The purpose of this innovation is to raise the glass transition temperature of all organic polyimide aerogel by use of tri-, tetra-, or poly-functional units in the structure to create a 3D covalently bonded network. Such cross-linked polyimides typically have higher glass transition temperatures in excess of 300 400 C. In addition, the reinforcement provided by a 3D network should improve mechanical stability, and prevent shrinkage on supercritical fluid extraction. The use of tri-functional aromatic or aliphatic amine groups in the polyimide backbone will provide such a 3D structure.

Panek, John↗

Development of an Autofluorescence Spectral Database for the Identification and Classification of Microbial Extremophiles

Extremophiles are microorganisms that have adapted to severe conditions that were once considered devoid of life. The extreme settings in which these organisms flourish on earth resemble many extraterrestrial environments. Identification and classification of extremophiles in situ (without the requirement for excessive handling and processing) can provide a basis for designing remotely operated instruments for extraterrestrial life exploration. An important consideration when designing such experiments is to prevent contamination of the environments. We are developing a reference spectral database of autofluorescence from microbial extremophiles using long-UV excitation (405 nm). Aromatic compounds are essential components of living systems, and biological molecules such as aromatic amino acids, nucleotides, porphyrins and vitamins can also exhibit fluorescence under long-UV excitation conditions. Autofluorescence spectra were obtained from a confocal microscope that additionally allowed observations of microbial geometry and motility. It was observed that all extremophiles studied displayed an autofluorescence peak at around 470 nm, followed by a long decay that was species specific. The autofluorescence database can potentially be used as a reference to identify and classify past or present microbial life in our solar system.

Sabanayagam, Chandran↗

Organic Carbon Features Identified in the Nakhla Martian Meteorite

We report, for the first time, the identification of specific carbonaceous phases, present within iddingsite alteration zones of the Nakhla meteorite that possess discrete, well defined, structurally coherent morphologies. These structures bear superficial similarity to the carbonaceous nanoglobules [1] found in primitive chondrites interplanetary dust particles, although they are an order-of-magnitude larger in size. Introduction: It has been known for many years that some members of the Martian meteorite clan contain organic matter [e.g., 2-4]. Based on both isotopic measurements [5] and circumstantial observations [4] (e.g., the similarity organic signatures present in both Antarctic finds and non-Antarctic falls) a credible argument has been made for a preterrestrial origin for the majority of these organics. The Nakhla meteorite is of particular interest in that it has been shown to contain both an acid-labile organic fraction as well as an acid-insoluble high molecular weight organic component [4]. Pyrolysis-gas chromatography-mass spectrometry of the latter component indicates it to be composed of aromatic and alkyl-aromatic functionalities bound into a macromolecule phase through ether linkages [4]. However, the spatial, textural and mineralogical associations of this carbonaceous macromolecular material have remained elusive [6].

Mckay, D. S.↗

Commercialization of LARC (TradeMark) -SI Polyimide Technology

LARC(TradeMark)-SI, Langley Research Center- Soluble Imide, was developed in 1992, with the first patent issuing in 1997, and then subsequent patents issued in 1998 and 2000. Currently, this polymer has been successfully licensed by NASA, and has generated revenues, at the time of this reporting, in excess of $1.4 million. The success of this particular polymer has been due to many factors and many lessons learned to the point that the invention, while important, is the least significant part in the commercialization of this material. Commercial LARC(TradeMark)-SI is a polyimide composed of two molar equivalents of dianhydrides: 4,4 -oxydiphthalic anhydride (ODPA), and 3,3 ,4,4 -biphenyltetracarboxylic dianhydride (BPDA) and 3,4 -oxydianiline (3,4 -ODA) as the diamine. The unique feature of this aromatic polyimide is that it remains soluble after solution imidization in high-boiling, polar aprotic solvents, even at solids contents of 50-percent by weight. However, once isolated and heated above its T(sub g) of 240 C, it becomes insoluble and exhibits high-temperature thermoplastic melt-flow behavior. With these unique structure property characteristics, it was thought this would be an advantage to have an aromatic polyimide that is both solution and melt processable in the imide form. This could potentially lead to lower cost production as it was not as equipment- or labor-intensive as other high-performance polyimide materials that either precipitate or are intractable. This unique combination of properties allowed patents with broad claim coverage and potential commercialization. After the U.S. Patent applications were filed, a Small Business Innovation Research (SBIR) contract was awarded to Imtec, Inc. to develop and supply the polyimide to NASA and the general public. Some examples of demonstration parts made with LARC(TradeMark)-SI ranged from aircraft wire and multilayer printed-circuit boards, to gears, composite panels, supported adhesive tape, composite coatings, cookware, and polyimide foam. Even with its unique processing characteristics, the thermal and mechanical properties were not drastically different from other solution or meltprocessable polyimides developed by NASA. LARC(TradeMark)-SI risked becoming another interesting, but costly, high-performance material.

Bryant, Robert G.↗