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Polymers are prepared with terminal functional groups by reacting a compound selected from the group consisting of lithium p-lithiophenoxide and tetrabutylammonium p-lithiophenoxide as an initiator with material such as butadiene. The resulting functionally terminated new polymers are then capable of reacting with coupling agents to form star polymers.
This invention is an improvement in standard polymerizations procedures, i.e., addition-type and step-growth type polymerizations, wherein monomers are reacted to form a growing polymer chain. The improvement includes employing an effective amount of a trifunctional monomer (such as a trifunctional amine anhydride, or phenol) in the polymerization procedure to form a mixture of polymeric materials consisting of branced polymers, star-shaped polymers, and linear polymers. This mixture of polymeric materials has a lower melt temperature and a lower melt viscosity than corresponding linear polymeric materials of equivalent molecular weight.
Primitive Solar System materials (e.g. chondrites. IDPs, the Stardust sample) show large variations in isotopic composition of the major volatiles (H, C, N, and O ) even within samples, witnessing to various degrees of processing in the protosolar nebula. For ex~ ample. the very pronounced D enhancements observed in IDPs [I] . are only generated in the cold. dense component of the interstellar medium (ISM), or protoplanetary disks, through ion-molecule reactions in the presence of interstellar dust. If this isotopic anomaly has an interstellar origin, this leaves open the possibility for preservation of other isotopic signatures throughout the form ation of the Solar System. The most common form of carbon in the ISM is CO molecules, and there are two potential sources of C-13 fractionation in this reservoir: low temperature chemistry and selective photodissociation. While gas-phase chemistry in cold interstellar clouds preferentially incorporates C-13 into CO [2], the effect of self-shielding in the presence of UV radiation instead leads to a relative enhancement of the more abundant isotopologue, 12CO. Solar System organic material exhibit rather small fluctuations in delta C-13 as compared to delta N-15 and delta D [3][1], the reason for which is still unclear. However, the fact that both C-13 depleted and enhanced material exists could indicate an interstellar origin where the two fractionation processes have both played a part. Formaldehyde (H2CO) is observed in the gas-phase in a wide range of interstellar environments, as well as in cometary comae. It is proposed as an important reactant in the formation of more complex organic molecules in the heated environments around young stars, and formaldehyde polymers have been suggested as the common origin of chondritic insoluable organic matter (IOM) and cometary refractory organic solids [4]. The relatively high gas-phase abundance of H2CO observed in molecular clouds (10(exp- 9) - 10(exp- 8) relative to H2) makes it feasible to observe its less common isotopologues. As a step in our investigation of C-13 fractionation patterns in the ISM, we here present comparisons between observations of the C-13 fraction in formaldehyde, and chemical fractionation models.
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.
Considerable attention has been directed towards acetylene terminated oligomers over the last 20 years' and recent work has focused on phenylethynyl terminated imide (PETI) oligomers. These reactive oligomers possess several features which make them attractive candidates for use as composite matrices and adhesives. The phenylethynyl group can be readily incorporated into many different functionalized oligomers. The reactive oligomers possess relatively low melt viscosities and thermally cure without the evolution of volatile by-products. Once cured, they typically display high glass transition temperatures (Tgs), excellent solvent resistance and high mechanical properties. new modified phenylethynyl-terminated imide (LaRC MPEI) oligomers were synthesized at various molecular weights utilizing a small amount of trifunctional amine. As long as the amount of triamine is relatively small, this approach produces a mixture of linear, star-shaped and branched polymer chains that has lower melt and solution viscosity than an equivalent molecular weight linear phenylethynyl terminated imide oligomers. The work reported herein involves the synthesis and characterization of a copolymer using this approach and the preparation of blends utilizing a phenylethynyl containing reactive plasticizer of lower molecular weight called LaRC LV-121. The chemistry and properties of this new MPEI as well as some blends of MPEI with LV-121, are presented and compared to the linear version, LARC-PETI-5.
GENOA-PFA, marketed currently by Alpha Star Corporation, is an enhanced commercial version of the Composite Durability Structural Analysis (CODSTRAN) computer program that was originally developed in-house at NASA Glenn Research Center specifically for polymer-matrix composite structures. Alpha Star Corporation and the University of Clarkson ha ve made substantial developments to the code under the NASA Small Bus iness Innovation Research and University Grant support. The code won the NASA Software of the year award in 1999 and was given the 2000 R&D 100 Award. The current GENOA-PFA can simulate the initiation and pro gression of damage, ultimately leading to global fracture in advanced composite structures under various loading and environmental conditi ons. It offers a number of capabilities beyond those of programs developed previously for similar purposes; these capabilities make GENOA-P FA preferable for use in analyzing the durability and damage toleranc e of complex aero and space structures that have fiber reinforcements formed as two- and even three-dimensional weaves and braids.
As an ongoing effort to develop structural adhesives for high performance aerospace applications, recent work has focused on phenylethynyl terminated imide (PETI) oligomers. The work reported herein involves the synthesis and characterization of a series of phenylethynyl containing oligomers designated LARC (TM) MPEI (Modified Phenylethynyl Terminated Polyimide). These oligomers contain mixtures of linear, branched and star-shaped molecules. The fully imidized polymers exhibited minimum melt viscosity as low as 600 poise at 335 C. Ti/Ti lap shear specimens processed at 288 C under 15 psi showed tensile shear strength of approx. 6000 psi and 5200 psi at ambient and 350 F temperatures, respectively. The chemistry and properties of these new MPEIs are presented and compared to an optimized linear PETI, LaRC(Tm) -PETI-5.
As an ongoing effort to develop structural adhesives for high-performance aerospace applications, recent work has focused on phenylethynyl terminated imide (PETI) oligomers. The work reported herein involves the synthesis and characterization of a series of phenylethynyl containing oligomers designated LARC(TM) MPEI (modified phenylethynyl imide). These oligomers presumably contain mixtures of linear, branched and star-shaped molecules. The fully imidized polymers exhibited minimum melt viscosities as low as 600 poise at 335 C, significantly lower than equivalent molecular weight linear materials. Ti/Ti lap shear specimens processed at 288 C under 15 psi showed tensile shear strengths as high as approx. 6000 psi and 5200 psi at ambient temperature and 177 C respectively. The chemistry and properties of these new MPEIs are presented and compared with an optimized linear PETI, LARC(TM)PETI-5.
High-performance polymers that have improved processing characteristics, and a method of making them, have been invented. One of the improved characteristics is low (relative to corresponding prior polymers) melt viscosities at given temperatures. This characteristic makes it possible to utilize such processes as resin-transfer molding and resin-film infusion and to perform autoclave processing at lower temperatures and/or pressures. Another improved characteristic is larger processing windows that is, longer times at low viscosities. Other improved characteristics include increased solubility of uncured polymer precursors that contain reactive groups, greater densities of cross-links in cured polymers, improved mechanical properties of the cured polymers, and greater resistance of the cured polymers to chemical attack. The invention is particularly applicable to poly(arylene ether)s [PAEs] and polyimides [PIs] that are useful as adhesives, matrices of composite materials, moldings, films, and coatings. PAEs and PIs synthesized according to the invention comprise mixtures of branched, linear, and star-shaped molecules. The monomers of these polymers can be capped with either reactive end groups to obtain thermosets or nonreactive end groups to obtain thermoplastics. The synthesis of a polymeric mixture according to the invention involves the use of a small amount of a trifunctional monomer. In the case of a PAE, the trifunctional monomer is a trihydroxy- containing compound for example, 1,3,5-trihydroxybenzene (THB). In the case of a PI, the trifunctional monomer is a triamine for example, triamino pyrimidine or melamine. In addition to the aforementioned trifunctional monomer, one uses the difunctional monomers of the conventional formulation of the polymer in question (see figure). In cases of nonreactive end caps, the polymeric mixtures of the invention have melt viscosities and melting temperatures lower than those of the corresponding linear polymers of equal molecular weights. The lower melting temperatures and melt viscosities provide larger processing windows. In cases of reactive end caps, the polymeric mixtures of the invention have lower melt viscosities before curing and the higher cross-link densities after curing (where branching in the uncured systems would become cross-links in the cured systems), relative to the corresponding linear polymers of equal molecular weights. The greater cross-link densities afford increased resistance to chemical attack and improved mechanical properties.
Atomic oxygen is one of the predominant constituents of Earth's upper atmosphere. It is created by the photodissociation of molecular oxygen (O2) into single O atoms by ultraviolet radiation. It is chemically very reactive because a single O atom readily combines with another O atom or with other atoms or molecules that can form a stable oxide. The effects of atomic oxygen on the external surfaces of spacecraft in low Earth orbit can have dire consequences for spacecraft life, and this is a well-known and much studied problem. Much less information is known about the effects of atomic oxygen on the internal surfaces of spacecraft. This degradation can occur when openings in components of the spacecraft exterior exist that allow the entry of atomic oxygen into regions that may not have direct atomic oxygen attack but rather scattered attack. Openings can exist because of spacecraft venting, microwave cavities, and apertures for Earth viewing, Sun sensors, or star trackers. The effects of atomic oxygen erosion of polymers interior to an aperture on a spacecraft were simulated at the NASA Glenn Research Center by using Monte Carlo computational techniques. A two-dimensional model was used to provide quantitative indications of the attenuation of atomic oxygen flux as a function of the distance into a parallel-walled cavity. The model allows the atomic oxygen arrival direction, the Maxwell Boltzman temperature, and the ram energy to be varied along with the interaction parameters of the degree of recombination upon impact with polymer or nonreactive surfaces, the initial reaction probability, the reaction probability dependence upon energy and angle of attack, degree of specularity of scattering of reactive and nonreactive surfaces, and the degree of thermal accommodation upon impact with reactive and non-reactive surfaces to be varied to allow the model to produce atomic oxygen erosion geometries that replicate actual experimental results from space. The degree of erosion of various interior locations was compared with the erosion that would occur external to the spacecraft. Results of one cavity model indicate that, at depths into a two-dimensional cavity that are equal to 10 cavity widths, the erosion on the walls of the cavity is less than that on the top surface by over 2 orders of magnitude. Wall erosion near the surface of a cavity depends on which wall is receiving direct atomic oxygen attack. However, deep in the cavity little difference is present. Testing of various cavity models such as these gives spacecraft designers an indication of the level of threat to sensitive interior surfaces for different geometries. Even though the Monte Carlo model is two-dimensional, it can be used to provide qualitative information about spacecraft openings that are three-dimensional by offering reasonable insight as to the nature of the attenuation of damage that occurs within a spacecraft in low Earth orbit. As shown, there is more erosion on the side seeing direct atomic oxygen attack until a depth of approximately 5 times the width of the opening, where the erosion is the same on both sides.
Long description. Illustrations of discotic liquid crystals, rod-coil polymers, lithium-ion conducting channel dilithium phthalocyanine (Li2Pc) from top and side, novel star polyethylene oxide structures, composite polyethylene oxide materials (showing polyethylene oxide + lithium salt, carbon atoms and oxygen atoms), homopolyrotaxanes, and diblock copolymers In fiscal year 2000, NASA established a program to develop the next generation, lithium-based, polymer electrolyte batteries for aerospace applications. The goal of this program, known as Polymer Energy Rechargeable Systems (PERS), is to develop a space-qualified, advanced battery system embodying polymer electrolyte and lithium-based electrode technologies and to establish world-class domestic manufacturing capabilities for advanced batteries with improved performance characteristics that address NASA s future aerospace battery requirements.
Carborane-substituted polyphosphazenes were prepared by the thermal polymerization of phenyl-carboranyl pentachlorocylotriphosphazene. Successive isothermal vacuum pyrolyses were conducted on the polymer and examined for structural changes by infrared spectroscopy. The degradation products were ascertained by gas chromatography-mass spectrometric analysis. It was found that the presence of the carborane group improves the thermal stability of the polymer by retarding the ring-chain equilibrium processes of decomposition. Previously announced in STAR as A83-21034
Cationic polyelectrolytes are formed by the polymerization in absence of oxygen of a monomer of the general formula: ##STR1## where x is 3 or more than 6 and Z is I, Br or Cl to form high charge density linear polymers. Segments of the linear polymer may be attached to or formed in the presence of polyfunctional reactive tertiary amines or halogen polymeric substrates or polyfunctional lower molecular reactive polyfunctional substrates to form branched or star polyelectrolytes by a quaternization polymerization reaction.
The topics include: 1) Virtual Reality Technology as a Tool to Enhance Collaboration Between Space Exploration and Public Outreach: The Case Using the Mars Exploration Rover Images; 2) Atmospheric Electron-induced X-Ray Spectrometer (AEXS) Instrument Development; 3) Impact of Low Thermal Conductivity Layers on the Bulk Conductivity of a Martian Crustal Column; 4) Impacting Classroom Teachers Through Long-Term Professional Development; 5) Oxygen, Ca, and Ti Isotopic Compositions of Hibonite-bearing Inclusions; 6) Phenomenological Excitation Functions of Xe Isotopes with Protons on Nuclei of Cs, La and Ce; 7) Double-Diffusive Convection and Other Modes of Salinity-modulated Heat and Material Transport in Europa s Ocean; 8) Slope Morphologies of the Hellas Mensae Constructs, Eastern Hellas Planitia, Mars; 9) Development of Polygonal Thermal Contraction Patterns in a South Polar Trough, Mars 3 Years of Observations; 10) Martian Relevance of Dehydration and Rehydration in the Mg-Sulfate System; 11) Formation of Martian Volcanic Provinces by Lower Mantle Flushing? 12) Can Glasses Help Us to Unravel the Origin of Barred Olivine Chondrules? 13) Loki Patera: A Magma Sea Story; 14) Compositions of Partly Altered Olivine and Replacement Serpentine in the CM2 Chondrite QUE93005; 15) Model of Light Scattering by Lunar Regolith at Moderate Phase Angles: New Results; 16) Radiation Resistance of a Silicone Polymer Grease Based Regolith Collector for the HERA Near-Earth Asteroid Sample Return Mission; 17) Analysis of the Tectonic Lineaments in the Ganiki Planitia (V14) Quadrangle, Venus; 18) Nanometer-sized Diamonds from AGB Stars; 19) Quantifying Exact Motions Along Lineaments on Europa; 20) Geometry of Thrust Faults Beneath Amenthes Rupes, Mars; 21) Mapping of the Physical Characteristics and Mineral Composition of a Superficial Layer of the Moon or Mars and Ultra-Violet Polarimetry from the Orbital Station; 22) Negative Searches for Evidence of Aqueous Alteration on Asteroid Surfaces; 23) What Processes Have Shaped Basalt Boulders on Earth and Mars? Studies of Feature Persistence Using Facet Mapping and Fractal Analysis; 24) The Popigai Fluidizites: Dense Water Inclusions in Lechatelierite; Evidence for Shock-generated Carbonate and Hydrous Silicate Melts; 25) Missing Xenon Problem and Climate of the Early Earth; and 26) More on Magnetic Spectra from Correlated Crustal Sources on Mars
This paper will review our current knowledge of circumstellar and interstellar dust from an astronomical point of view. About half of the interstellar dust volume consists of amorphous silicates. The remainder has to be made up of an carbonaceous component such as graphite, amorphous carbon (i.e., soot), Polycyclic Aromatic Hydrocarbon molecules (PAHs), and/or organic grain mantles (i.e., mixed polymers). The observational evidence for these components will be reviewed and their relative importance assessed. The emphasis will be on recent observations using the Infrared Space Observatory. Most of these dust components are formed in the outflows from stars in the late stages of their evolution (i.e., red giants, planetary nebulae, novae, supergiants, Wolf Rayet stars, and supernovae). Indeed, observation of such objects indicate an even richer spectrum of stardust components, including also SiC, MgS, and aluminates and crystalline silicates. These observations will be briefly discussed. The stardust budget of the galaxy will be reviewed and the relative importance of the various birth sites assessed. Finally, in recent years, isotopic composition studies have shown that some circumstellar and interstellar dust grains have been incorporated into solar system bodies such as planetary dust particles and meteorites without totally losing their identity. Among the components identified are SiC, graphite, diamonds, PAHs, aluminum oxides, as well as various trace element carbides. Studies of this kind have opened up a new window on the composition and structure of interstellar dust. These different sources of information on interstellar and circumstellar dust will be briefly contrasted.
In the last two decades, high temperature polyimide matrix composites have found broad applications in aerospace structural components, due to their high specific modulus and high specific strength. As matrix resins, aromatic polyimides exhibit exceptional thermal stability and mechanical properties. However, their rodlike structures often result in poor solubility in most common organic solvents, as well as high melt temperature and melt viscosity, making them difficult to process. To overcome this difficulty, flexible linkages including O, SO2 or CH2 non coplanar biphenyl moieties, bulky lateral substituents, and crankshaft structures are often incorporated into the polymer backbones. Addition-curing of low molecular weight polyimides (resins) is another approach to improve processability. One of the most successfully developed materials has been PMR-15 (Polymerization of Monomer Reactants, molecular weight of 1500 g/mol), because of its good combination of thermal and mechanical properties and ease of processability. However, due to the high melt viscosity of PMR-type resins, use of more economical processing methods, such as resin transfer molding (RTM), is not possible. Recent research has focused on the incorporation of trifunctional monomers into addition-curing polyimides in an attempt to improve the processability of these polymers. The objective of this research is to use an aromatic triamine, 1,3,5 tris (4-aminophenoxy) benzene, to prepare new resin systems with starbranched structures. The glass transition temperatures (Tg's) and thermal oxidative stability TOS) of these polymers are compared to their linear counterparts and PMR-15.
This paper reports on an investigation of the concept of modifying the thermal performance of filled polymers through a minor compositional change (presently by coating the filler). The fire-safety of construction materials and the instability of solid rockets are used as examples. A theory is developed which shows that vast improvements are possible by controlling thermal conductivity. Experiments are described that show the weight loss and smoke density in the NBS smoke-density chamber of fiberglass-reinforced epoxy panels, and the instability trends of an AP-HTPB propellant fired in an L-Star rocket motor. The feasibility of tailoring thermal behavior to suit each particular need is demonstrated.
The chirality of organic molecules with the asymmetric location of group radicals was discovered in 1848 by Louis Pasteur during his investigations of the rotation of the plane of polarization of light by crystals of sodium ammonium paratartrate. It is well established that the amino acids in proteins are exclusively Levorotary (L-aminos) and the sugars in DNA and RNA are Dextrorotary (D-sugars). This phenomenon of homochirality of biological polymers is a fundamental property of all life known on Earth. Furthermore, abiotic production mechanisms typically yield recemic mixtures (i.e. equal amounts of the two enantiomers). When amino acids were first detected in carbonaceous meteorites, it was concluded that they were racemates. This conclusion was taken as evidence that they were extraterrestrial and produced by abiologically. Subsequent studies by numerous researchers have revealed that many of the amino acids in carbonaceous meteorites exhibit a significant L-excess. The observed chirality is much greater than that produced by any currently known abiotic processes (e.g. Linearly polarized light from neutron stars; Circularly polarized ultraviolet light from faint stars; optically active quartz powders; inclusion polymerization in clay minerals; Vester-Ulbricht hypothesis of parity violations, etc.). This paper compares the measured chirality detected in the amino acids of carbonaceous meteorites with the effect of these diverse abiotic processes. IT is concluded that the levels observed are inconsistent with post-arrival biological contamination or with any of the currently known abiotic production mechanisms. However, they are consistent with ancient biological processes on the meteorite parent body. This paper will consider these chiral biomarkers in view of the detection of possible microfossils found in the Orgueil and Murchison carbonaceous meteorites. Energy dispersive x-ray spectroscopy (EDS) data obtained on these morphological biomarkers will be presented to show that the elemental compositions of these morphological biomarkers are not consistent with the compositions expected for modern (i.e. post-arrival) biological contaminants.