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At least 37 records · Page 2

Molecules with enhanced electronic polarizabilities based on defect-like states in conjugated polymers

Highly conjugated organic polymers typically have large non-resonant electronic susceptibilities, which give the molecules unusual optical properties. To enhance these properties, defects are introduced into the polymer chain. Examples include light doping of the conjugated polymer and synthesis, conjugated polymers which incorporate either electron donating or accepting groups, and conjugated polymers which contain a photoexcitable species capable of reversibly transferring its electron to an acceptor. Such defects in the chain permit enhancement of the second hyperpolarizability by at least an order of magnitude.

Beratan, David N.↗

Development of polysilsesquioxane composites

Polymer composites are increasingly being required to operate for prolonged durations at higher temperatures than in the past. Hence there have been increased efforts devoted to synthesizing and characterizing polymers capable of withstanding temperatures greater than 300 C for long periods. Several such organic polymers have been investigated in recent times. This research effort seeks to enquire if inorganic polymers can be utilized to provide the same result. Ceramics have long been recognized as providing superior thermal properties for demanding applications. However, the extremely high softening temperatures preclude their being shaped into complex shapes through melt processing techniques common to organic polymers. One approach towards solving this problem has been through the development of preceramic polymers. These are capable of being processed in the polymeric state with ease, and subsequently being pyrolyzed to ceramic structures. This experimental study is aimed at studying the feasibility of using preceramic polymers (that have not been subject to the pyrolysis step) as high performance composite matrices for high temperature applications. A preliminary study of this nature is not geared towards optimizing mechanical properties suitable for such composites. Rather, this study attempts to process such resins in composite form and suitably characterize their properties.

Srinivasan, K.↗

The polymer-like organic material in the Orgueil meteorite

Results are reported for analysis of polymeric organic material contained in powder from the Orgueil chondrite, using a stepwise high-vacuum pyrolysis-gas chromatography-mass spectrometry technique. Pyrolysis products obtained include a series of alkanes and alkenes to C8, an extensive series of alkylbenzene isomers, thiophene, alkylthiophenes, benzothiophene, acetonitrile, acrylonitrile, benzonitrile, acetone, and phenol. Most of these products are shown to be similar both qualitatively and quantitatively to those previously obtained from solvent-extracted Allende powder, indicating a basically aromatic and heteroaromatic polymer matrix with short aliphatic bridges or side chains. The production of acrylonitrile, acetonitrile, and benzonitrile (common breakdown products of amino acids) from the insoluble organic material is taken to suggest that amino acids exist in an insoluble form, perhaps as peptides, in the meteorite's polymeric component. Similarities between the structure of the Orgueil polymeric material and terrestrial kerogen are discussed which raise the possibility that both might have been produced in part by similar reactions.

Bandurski, E. L.↗

Effects of the Low Earth Orbital environment on spacecraft materials

Recession of organic-polymer-based surfaces due to oxidation by atomic oxygen, the major component of the LEO environment, was studied in Space Shuttle flights 5, 8, and 41-G to measure reaction rates and the effects of various parameters on reaction rates. Surface recession on the flights indicates reaction rates of 3 x10 to the minus 24th power cc atom for unfilled organic polymers. Application of these rates to Space Station-type exposure for main structural items indicates that as much as 0.075 cm of surface recession occurs in 30 yr. Because of the importance of this effect on Space Station systems, additional experiments are planned to obtain better reaction rate measurements ensuring and adequate data base for Space Station design.

Leger, L. J.↗

Effects of the low Earth orbital environment on spacecraft materials

It is evident from space flights during the last three years that the low Earth orbital (LEO) environment interacts with spacecraft surfaces in significant ways. One manifestation of these interactions is recession of, in particular, organic-polymer-based surfaces presumably due to oxidation by atomic oxygen, the major component of the LEO environment. Three experiments have been conducted on Space Shuttle flights 5, 8 and 41-G to measure reaction rates and the effects of various parameters on reaction rates. Surface recession on these flights indicates reaction efficiencies approximately 3 x 10(-24) cu cm/atoms for unfilled organic polymers. Of the metals, silver and osmium are very reactive. Effects on spacecraft or experiment surfaces can be evaluated using the derived reaction efficiencies and a definition of the total exposure to atomic oxygen. This exposure is obtained using an ambient density model, solar activity data and spacecraft parameters of altitude, attitude and operational date. Oxygen flux on a given surface is obtained from the ambient density and spacecraft velocity and can then be integrated to provide the total exposure or fluence. Such information can be generated using simple computational programs and can be converted to various formats. Overall, the extent of damage is strongly dependent on the type of surface and total exposure time.

Leger, L. J.↗

Evaluation of an electrochemical N2/H2 gas separator

A program was successfully completed to evaluate an electrochemical nitrogen/hydrogen (N2/H2) separator for use in a spacecraft nitrogen (N2) generator. Based on the technical data obtained a N2/H2 separator subsystem consisting of an organic polymer gas permeator first stage and an electrochemical second and third stage was estimated to have the lowest total spared equivalent weight, 257 kg (566 lb), for a 15 lb/day N2 generation rate. A pre-design analysis of the electrochemical N2/H2 separator revealed that its use as a first stage resulted in too high a power requirement to be competitive with the organic polymer membrane and the palladium-silver membrane separation methods. As a result, program emphasis was placed on evaluating the electrochemical. A parametric test program characterized cell performance and established second- and third-stage electrochemical N2/H2 separator operating conditions. A design verification test was completed on the second and third stages. The second stage was then successfully endurance tested for 200 hours.

Marshall, R. D.↗

Nonlinear optical thin films

A focused approach to development and evaluation of organic polymer films for use in optoelectronics is presented. The issues and challenges that are addressed include: (1) material synthesis, purification, and the tailoring of the material properties; (2) deposition of uniform thin films by a variety of methods; (3) characterization of material physical properties (thermal, electrical, optical, and electro-optical); and (4) device fabrication and testing. Photonic materials, devices, and systems were identified as critical technology areas by the Department of Commerce and the Department of Defense. This approach offers strong integration of basic material issues through engineering applications by the development of materials that can be exploited as the active unit in a variety of polymeric thin film devices. Improved materials were developed with unprecedented purity and stability. The absorptive properties can be tailored and controlled to provide significant improvement in propagation losses and nonlinear performance. Furthermore, the materials were incorporated into polymers that are highly compatible with fabrication and patterning processes for integrated optical devices and circuits. By simultaneously addressing the issues of materials development and characterization, keeping device design and fabrication in mind, many obstacles were overcome for implementation of these polymeric materials and devices into systems. We intend to considerably improve the upper use temperature, poling stability, and compatibility with silicon based devices. The principal device application that was targeted is a linear electro-optic modulation etalon. Organic polymers need to be properly designed and coupled with existing integrated circuit technology to create new photonic devices for optical communication, image processing, other laser applications such as harmonic generation, and eventually optical computing. The progression from microscopic sample to a suitable film-forming material in a working device is a complex, multifaceted endeavor. It requires close attention to maintaining the optical properties of the electro-optic active portion of the polymer while manipulating the polymer structure to obtain the desired secondary polymer properties.

Leslie, Thomas M.↗

Carbonaceous chondritic material in the solar system

Carbonaceous chondritic matrix material (CCMM) appears to be an important planet-forming unit in the mid-solar system, from the orbits of Mars to that of Uranus. The type specimen for CCMM is the low-temperature (400-500 K) assemblage of clay minerals, organic polymer, magnetite, and Ni-rich iron sulfides which constitutes the black, fine-grained matrix of primitive carbonaceous chondrites. Solar-system objects which appear to be partly or wholly made of CCMM are the satellites of Mars, most asteroids, interplanetary dust, and, perhaps, comets, satellites of the outer planets and the rings of Uranus. CCMM constituents probably formed by low-temperature reactions of higher-temperature condensates with the ambient solar composition gas, or in the case of the organic polymer, by reactions of gaseous species catalyzed by solids.

Wilkening, L. L.↗

Quantum chemical calculations for polymers and organic compounds

The relativistic effects of the orbiting electrons on a model compound were calculated. The computational method used was based on 'Modified Neglect of Differential Overlap' (MNDO). The compound tetracyanoplatinate was used since empirical measurement and calculations along "classical" lines had yielded many known properties. The purpose was to show that for large molecules relativity effects could not be ignored and that these effects could be calculated and yield data in closer agreement to empirical measurements. Both the energy band structure and molecular orbitals are depicted.

Lopez, J.↗

Static electricity of polymers reduced by treatment with iodine

Treating organic polymers with iodine improves the electrical conductivity. Diffusion enables products of desired properties to be custom formulated. This eliminates a buildup of static electricity and the need for fillers or bound metal salts.

Hermann, A. M.↗

Exobiology and the origin of life

Research supported wholly or in part by NASA is summarized, Topics covered include the molecular analysis of ultraviolet-photoproduced organic solids synthesized under simulated Jovian conditions; the molecular analysis of organic solids produced by electrical discharge in reducing atmospheres; the organic chemistry of interstellar grains; the spectra of possible organic solids present as aerosols in planetary atmospheres; far infrared studies of organic polymers of possible astrophysical interest; organic dust synthesized in reducing environments by ultraviolet radiation or electric discharge; the diffusion of galactic civilizations; eavesdropping on galactic civilizations; Lander imaging as a detector of life on Mars; and continuing puzzles about Mars. Bibliographic data is included for four additional publications not supported by NASA grant, but related to the objectives of the program.

Sagan, C.↗

Highly porous ceramic oxide aerogels having improved flexibility

Ceramic oxide aerogels having improved flexibility are disclosed. Preferred embodiments exhibit high modulus and other strength properties despite their improved flexibility. The gels may be polymer cross-linked via organic polymer chains to further improve strength properties, without substantially detracting from the improved flexibility. Methods of making such aerogels are also disclosed.

Meador, Mary Ann B.↗

Highly porous ceramic oxide aerogels having improved flexibility

Ceramic oxide aerogels incorporating periodically dispersed flexible linkages are provided. The flexible linkages impart greater flexibility than the native aerogels without those linkages, and have been shown to reduce or eliminate the need for supercritical CO.sub.2-mediated drying of the corresponding wet gels. The gels may also be polymer cross-linked via organic polymer chains that are attached to and extend from surface-bound functional groups provided or present over the internal surfaces of a mesoporous ceramic oxide particle network via appropriate chemical reactions.

Meador, Mary Ann B.↗

Polymer compositions suitable for use in enriched oxygen atmospheres

Three organic polymer systems are based on copolymer of chlorotrifluoroethylene, ethylene, and tin-based flame retardants. Fourth system is copolymer of chlorotrifluorethylene and tetrafluoroethylene. This system contains no stabilizers of flame retardant additives.

Schule, E. C.↗

Gas Sensor Test Chip

The use of organic polymers to detect gasses has been known for several years to be an effective means for gas detection via conductivity changes. These chemoresistors offer significant advantages over other gas detectors in that they operate near room temperature and thus can be used in compact, low-power applications.

organic polymers sheet resistance conduction aniso↗

A Structural and Molecular Approach for the Study Biomarkers

Investigation of the nucleation and growth of crystals in both abiotic and biotic systems is critical to seemingly diverse disciplines of geology, biology, environmental science, and astrobiology. While there are abundant studies devoted to the determination of the structure and composition of inorganic crystals, as well as to the development of thermodynamic and kinetic models, it is only recently that research efforts have been directed towards understanding mineralization in biological systems (i.e., biomineralization). Biomineralization refers to the processes by which living organisms form inorganic solids. Studies of the processes of biomineralization under low temperature aqueous conditions have focused primarily on magnetite forming bacteria and shell forming marine organisms. Many of the biological building materials consist of inorganic minerals (calcium carbonate, calcium phosphate, silica or iron oxide) intricately combined with organic polymers (like proteins). More recently, efforts have been undertaken to explore the nature of biological activities in ancient rocks. In the absence of well-preserved microorganisms or genetic material required for the polmerase chain reaction (PCR) method in molecular phylogenetic studies, using biominerals as biomarkers offers an alternative approach for the recognition of biogenic activity in both terrestrial and extraterrestrial environments. The primary driving force in biomineralization is the interaction between organic and inorganic phases. Thus, the investigation of the ultrastructure and the nature of reactions at the molecular level occurring at the interface between inorganic and organic phases is essential to understanding the processes leading to the nucleation and growth of crystals. It is recognized that crystal surfaces can serve as the substrate for the organization of organic molecules that lead to the formation of polymers and other complex organic molecules, and in discussions of the origins of life, is referred to as organic synthesis on mineral surfaces. Furthermore, it is suggested that the interaction between mineral surfaces and simple organic molecules resulted in the formation of amino acids, RNA, and perhaps other more complex molecules such as proteins. On the other hand, in natural systems, it is recognized that functional groups on cell walls or membranes of microorganisms serve as sites of nucleation and crystallization. The precise replication of biominerals with controlled structure, morphology, size and texture is not confined to higher organisms as it also occurs in primitive prokaryotic cells such as magnetotactic bacteria and cyanobacteria. This suggests that the principal strategies of biomineralization were established early on in the evolutionary history of organisms. It is critical, therefore, to search for common mechanisms within diverse biological systems. One such common factor is the capability for organization and self-assembly. Organic macromolecules such as proteins and lipids can aggregate and polymerize forming membranes or extracellular matrix. At the organic-inorganic interface, several factors such as lattice geometry, polarity, stereochemistry and topography may act in concert to control nucleation and growth of crystals. Although several models have been proposed that discuss the significance of these factors for biomineralization, no comprehensive experimental data are available. In contrast to crystallization in exclusively inorganic systems, the kinetics of reaction and structural relationships between organic and inorganic phases in biominerals or biomimetic material is poorly understood. For example, it is not clear if the concept of epitactic growth (geometrical matching of unit cells at the interface of a secondary crystal growing on a primary crystal) applies to organic-inorganic systems. In contrast to inorganic templates that often have a smooth and rigid surface that promotes epitactic growth, biological substrates are usually rough and result in a large degree of mismatch. It is apparent that factors controlling the reaction at the crystal-matrix interface are strongly dependent upon the nature of the substrate. Therefore, characterization of the assembled organic surface and surface structure of the inorganic phase is crucial to understanding the processes of biomineralization. The focus of our research is the investigation of the processes leading to the nucleation and growth of crystals on both natural and synthetic systems through an interdisciplinary approach that integrates molecular biology, morphology and mineralogy using advanced preparation and analytical techniques. We have studied run-products, particularly magnetite, siderite and other carbonates, that resulted from extracellular biomineralization by extremophiles isolated from a variety of extreme environments ranging from permafrost to hydrothermal vent systems. The results of this study are critical to recognizing biomarkers in terrestrial and extraterrestrial environments.

Thomas-Keprta, Kathie↗

Diels-Alder Trapping of Photochemically Generated o-Xylenols: Application in the Synthesis of Novel Organic Molecules and Polymers

Bis(o-xylenol) equivalents are useful synthetic intermediates in the construction of polymers and hydroxyl substituted organic molecules which can organize by hydrogen bonded self-assembly into unique supramolecular structures. These polymers and supramolecular materials have potential use as coatings and thin films in aerospace, electronic and biomedical applications.

Meador, Michael A.↗

Survey of inorganic polymers

A literature search was carried out in order to identify inorganic, metallo-organic, and hybrid inorganic-organic polymers that could serve as potential matrix resins for advanced composites. The five most promising candidates were critically reviewed and recommendations were made for the achievement of their potential in terms of performance and cost. These generic polymer classes comprise: (1) Poly(arylsil sesquioxanes); (2) Poly(silyl arylene siloxanes); (3) Poly(silarylenes); (4) Poly(silicon-linked ferrocenes); and (5) Poly(organo phosphazenes). No single candidate currently possesses the necessary combination of physicomechanical properties, thermal stability, processability, and favorable economics. The first three classes exhibit the best thermal performance. On the other hand, poly (organo phosphazenes), the most extensively studied polymer class, exhibit the best combination of structure-property control, processability, and favorable economics.

Gerber, A. H.↗