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NASA NTRS2010

Co-polymer films for sensors

Embodiments include a sensor comprising a co-polymer, the co-polymer comprising a first monomer and a second monomer. For some embodiments, the first monomer is poly-4-vinyl pyridine, and the second monomer is poly-4-vinyl pyridinium propylamine chloride. For some embodiments, the first monomer is polystyrene and the second monomer is poly-2-vinyl pyridinium propylamine chloride. For some embodiments, the first monomer is poly-4-vinyl pyridine, and the second monomer is poly-4-vinyl pyridinium benzylamine chloride. Other embodiments are described and claimed.

Ryan, Margaret A.↗

NASA NTRS2012

Co-polymer Films for Sensors

Ryan, Margaret A.↗

NASA NTRS2004

Montmorillonite, oligonucleotides, RNA and origin of life

Na-montmorillonite prepared from Volclay by the titration method facilitates the self-condensation of ImpA, the 5'-phosphorimidazolide derivative of adenosine. As was shown by AE-HPLC analysis and selective enzymatic hydrolysis of products, oligo(A)s formed in this reaction are 10 monomer units long and contain 67% 3',5'-phosphodiester bonds (Ferris and Ertem, 1992a). Under the same reaction conditions, 5'-phosphorimidazolide derivatives of cytidine, uridine and guanosine also undergo self-condensation producing oligomers containing up to 12-14 monomer units for oligo(C)s to 6 monomer units for oligo(G)s. In oligo(C)s and oligo(U)s, 75-80% of the monomers are linked by 2',5'-phosphodiester bonds. Hexamer and higher oligomers isolated from synthetic oligo(C)s formed by montmorillonite catalysis, which contain both 3',5'- and 2',5'-linkages, serve as catalysts for the non-enzymatic template directed synthesis of oligo(G)s from activated monomer 2-MeImpG, guanosine 5'-phospho-2-methylimidazolide (Ertem and Ferris, 1996). Pentamer and higher oligomers containing exclusively 2',5'-linkages, which were isolated from the synthetic oligo(C)s, also serve as templates and produce oligo(G)s with both 2',5'- and 3',5'-phosphodiester bonds. Kinetic studies on montmorillonite catalyzed elongation rates of oligomers using the computer program SIMFIT demonstrated that the rate constants for the formation of oligo(A)s increased in the order of 2-mer < 3-mer < 4-mer ... < 7-mer (Kawamura and Ferris, 1994). A decameric primer, dA(pdA)8pA bound to montmorillonite was elongated to contain up to 50 monomer units by daily addition of activated monomer ImpA to the reaction mixture (Ferris, Hill and Orgel, 1996). Analysis of dimer fractions formed in the montmorillonite catalyzed reaction of binary and quaternary mixtures of ImpA, ImpC, 2-MeImpG and ImpU suggested that only a limited number of oligomers could have formed on the primitive Earth rather than equal amounts of all possible isomers (Ertem and Ferris, 2000). Formation of phosphodiester bonds between mononucleotides by montmorillonite catalysis is a fascinating discovery, and a significant step forward in efforts to find out how the first RNA-like oligomers might have formed in the course of chemical evolution. However, as has been pointed out in several publications, these systems should be regarded as models rather than a literal representation of prebiotic chemistry (Orgel, 1998; Joyce and Orgel, 1999; Schwartz, 1999).

RNA/chemical synthesis↗

NASA NTRS2007

Method for nanoencapsulation of aerogels and nanoencapsulated aerogels produced by such method

A method for increasing the compressive modulus of aerogels comprising: providing aerogel substrate comprising a bubble matrix in a chamber; providing monomer to the chamber, the monomer comprising vapor phase monomer which polymerizes substantially free of polymerization byproducts; depositing monomer from the vapor phase onto the surface of the aerogel substrate under deposition conditions effective to produce a vapor pressure sufficient to cause the vapor phase monomer to penetrate into the bubble matrix and deposit onto the surface of the aerogel substrate, producing a substantially uniform monomer film; and, polymerizing the substantially uniform monomer film under polymerization conditions effective to produce polymer coated aerogel comprising a substantially uniform polymer coating substantially free of polymerization byproducts.Polymer coated aerogel comprising aerogel substrate comprising a substantially uniform polymer coating, said polymer coated aerogel comprising porosity and having a compressive modulus greater than the compressive modulus of the aerogel substrate, as measured by a 100 lb. load cell at 1 mm/minute in the linear range of 20% to 40% compression.

Sullivan, Thomas A.↗

NASA NTRS1996

Relative Rates for Plasma Homo- and Copolymerizations of Olefins in a Homologous Series of Fluorinated Ethylenes

The relative rates of plasma (co)polymerizations of ethylene, vinyl fluoride, vinylidene fluoride, trifluoroethylene and tetrafluoroethylene (VF(sub x); x = 0-4, respectively) were determined in an rf, capacitively coupled, tubular reactor with external electrodes using identical plasma parameters. The averages of deposition rates obtained by both microgravimetry and ellipsometry were plotted versus the F/C ratios of the monomers or monomer blends. The deposition rates for VF(sub x)(x = 1-3) and 20 monomer blends were all located above a straight line joining the rates for VF(sub 0) and VF(sub 4), following a concave-downward plot of deposition rate versus F/C ratio similar to that reported previously for VF(sub 0)/VF(sub 4) blends. The deposition rates for VF(sub m)/VF(sub n) blends (m = 3 or 4; n = 0-2) were all greater than expected for non-interacting monomers; those for VF(sub 0)/VF(sub 2) and VF(sub 1)/VF(sub 2) blends were all lower than expected; while those for VF(sub 0)/VF(sub 1) and VF(sub 3)/VF(sub 4) blends fen on a straightline plot versus F/C ratio, indicative of apparent non-interaction between monomers. The mechanisms for plasma (co)polymerizations of VF(sub x) monomers responsible for the wide range of relative deposition rates remain to be elucidated.

Golub, Morton A.↗

NASA NTRS2005

High-Performance Polymers Having Low Melt Viscosities

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.

Jensen, Brian J.↗

NASA NTRS2023

The Polarimetric Radar Scattering Properties of Oriented Aggregates

The scattering properties of aggregates are studied herein. Early aggregates (<7 monomers) of branched planar crystals and mature aggregates (up to 100 monomers) of columns are randomly generated with varying assumptions about the monomer attachment processes and the orientation behavior during collection. The resulting physical properties of the aggregates correspond well with prior in situ and retrieved sizes and shapes. Assumed azimuthally uniform orientations during collection and monomer pivoting upon attachment resulted in flatter and denser aggregates. The column aggregates had lower density and more spherical shapes than the branched planar crystal aggregates. The scattering properties were calculated using the discrete dipole approximation for a set of orientation angles and transformed to spectral coefficients representing modes of orientation angle variability. The zeroth- and second-order coefficients dominate this variability, with the zeroth-order coefficients representing the scattering properties for randomly oriented particles. The second-order coefficients for backscatter showed differences between horizontal and vertical polarization increasing with density, and these coefficients for specific differential phase increase with both mass and density. Similarly, coefficients for the copolar covariance decreased with density. Rapid changes in the contributions to the radar moments from the second-order coefficients from low to moderate density were observed, likely due to the increasing presence of horizontally aligned monomers in the aggregate structure. Differences in how differential reflectivity and correlation coefficient evolve with the orientation distribution parameters suggest that these measurements, along with specific differential phase and reflectivity, provide complementary information about aggregate sizes, shapes, and orientation distributions.

Cloud microphysics↗

NASA NTRS1978

Heat resistant polymers of oxidized styrylphosphine

Homopolymers, copolymers and terpolymers of a styrene based monomer are prepared by polymerizing at least one oxidized styrylphosphine monomer or by polymerizing p-diphenylphosphinestyrene and then oxidizing the polymerized monomer with an organoazide. Copolymers can also be prepared by copolymerizing styrene with at least one oxidized styrylphosphine monomer. Flame resistant vinyl based polymers whose degradation products are non toxic and non corrosive are obtained.

Paciorek, K. J. L.↗

NASA NTRS1979

Compound oxidized styrylphosphine

A process is described for preparing flame resistant, nontoxic vinyl polymers which contain phosphazene groups and which do not emit any toxic or corrosive products when they are oxidatively degraded. Homopolymers, copolymers, and terpolymers of a styrene based monomer are prepared by polymerizing at least one oxidized styrylphosphine monomer from a group of organic azides, or by polymerizing p-diphenylphosphinestyrene and then oxidizing that monomer with an organoazide from the group of (C6H5)2P(O)N3, (C6H5O)2P(O)N3, (C6H5)2C3N3(N3), and C6H5C3N3(N3)2. Copolymers can also be prepared by copolymerizing styrene with at least one oxidized styrylphosphine monomer.

Paciorek, K. J. L.↗

NASA NTRS1979

Synthesis of perfluoroalkylether oxadiazole elastomers

A method for the simultaneous chain extension and crosslinking of perfluoroalkylethers which yields a thermally stable perfluoroalkylether oxadiazole elastomer crosslinked by trifunctional perfluoroalkylether-1,3,5-triazine is reported. In the preparation, hydroxylamine crystals prepared from hydroxylamine hydrochloride to which sodium butoxide had been added is mixed with perfluoroalkylether dinitrile to obtain the monomer, as the nitrile is converted to amidoxime. Monomers are heated at 140 to 200 C to form poly(perfluoroalkylether oxadiazole) with a 1,2,4-oxadiazole structure by a step-growth polymerization reaction. Simultaneous chain extension and crosslinking are observed to occur when the purified monomer is heated directly and when the remaining nitrile in the monomer is allowed to react with excess ammonia to form the corresponding amidine, which is then heated. Weight loss studies show the thermal stability of the perfluoroalkylether elastomer to be generally better than fluorosilicone or polyester elastomers, especially in air, indicating its potential usefulness for high-performance elastomeric applications.

Rosser, R. W.↗

NASA NTRS1984

Homogeneous reactions of hydrocarbons, silane, and chlorosilanes in radiofrequency plasmas at low pressures

The ion-molecule and radical-molecule mechanisms are responsible for the dissociation of hydrocarbon, silane, and chlorosilane monomers and the formation of polymerized species, respectively, in an RF plasma discharge. In a plasma containing a mixture of monomer and argon the rate-determining step for both dissociation and polymerization is governed by an ion-molecule type of interaction. Adding hydrogen or ammonia to the monomer-argon mixture transforms the rate-determining step from an ion-molecule interaction to a radical-molecule interaction for both monomer dissociation and polymerization.

Avni, R.↗

NASA NTRS1984

Radical and ion molecule mechanisms in the polymerization of hydrocarbons and chlorosilanes in RF plasmas at low pressures ( 1.0 torr)

The ion-molecule and the radical-molecule mechanisms are responsible for the dissociation of hydrocarbons, and chlorosilane monomers and the formation of polymerized species, respectively, in the plasma state of a RF discharge. In the plasma, of a mixture of monomer with Ar, the rate determining step for both dissociation and polymerization is governed by an ion-molecular type interaction. Additions of H2 or NH3 to the monomer Ar(+) mixture transforms the rate determining step from an ion-molecular interaction to a radical-molecule type interaction for both monomer dissociation and polymerization processes.

Avni, R.↗

NASA NTRS1984

Toughening mechanism in elastomer-modified epoxy resins, part 2

The role of matrix ductility on the toughenability and toughening mechanism of elastomer-modified DGEBRA epoxies was investigated. Matrix ductility was varied by using epoxide resins of varying epoxide monomer molecular weights. These epoxide resins were cured using 4,4' diaminodiphenyl sulfone (DDS) and, in some cases, modified with 10% HYCAR(r)CTBN 1300X8. Fracture roughness values for the neat epoxies were found to be almost independent on the monomer molecular weight of the epoxide resin used. However, it was found that the fracture toughness of the elastomer-modified epoxies was very dependent upon the epoxide monomer molecular weight. Tensile dilatometry indicated that the toughening mechanism, when present, is similar to the mechanisms found for the piperidine cured epoxies in Part 1. SEM and OM corroborate this finding. Dynamic mechanical studies were conducted to shed light on the toughenability of the epoxies. The time-dependent small strain behavior of these epoxies were separated into their bulk and shear components. The bulk component is related to brittle fracture, whereas the shear component is related to yielding. It can be shown that the rates of shear and bulk strain energy buildup for a given stress are uniquely determined by the values of Poisson's ratio, nu. It was found that nu increases as the monomer molecular weight of the epoxide resin used increases. This increase in nu can be associated with the low temperature beta relaxation. The effect of increasing cross-link density is to shift the beta relaxation to higher temperatures and to decrease the magnitude of the beta relaxation. Thus, increasing cross-link density decreases nu and increases the tendency towards brittle fracture.

Yee, A. F.↗

NASA NTRS1984

Radical molecule and ion-molecule mechanisms in the polymerization of hydrocarbons and chlorosilanes in R.F. plasmas at low pressures (below 1.0 Torr)

Avni, R.↗

NASA NTRS1992

Synthesis, vapor growth, polymerization, and characterization of thin films of novel diacetylene derivatives of pyrrole. The use of computer modeling to predict chemical and optical properties of these diacetylenes and poly(diacetylenes)

In the present work two diacetylene derivatives of pyrrole which are predicted by semiempirical AM1 calculations to have very different properties, are synthesized; the polymerizability of these diacetylenes in the solid state is determined, and the results are compared to the computer predictions. Diacetylene 1 is novel in that the monomer is a liquid at room temperature; this may allow for the possibility of polymerization in the liquid state as well as the solid state. Thin poly(diacetylene) films are obtained from compound 1 by growing films of the monomer using vapor deposition and polymerizing with UV light; these films are then characterized. Interestingly, while the poly(diacetylene) from 1 does not possess good nonlinear optical properties, the monomer exhibits very good third-order effects (phase conjugation) in solution. Dilute acetone solutions of the monomer 1 give intensity-dependent refractive indices on the order of 10 exp -6 esu; these are 10 exp 6 times better than for CS2.

Paley, M. S.↗

NASA NTRS1991

Temperature dependence of electronic energy transfer and quenching in copolymer films of styrene and 2-(2'-hydroxy-5'-vinylphenyl)-2H-benzotriazole

Quenching of the emission of both the polystyrene monomer and the excimer for a series of varying composition copolymer films of styrene and 2-(2'-hydroxy-5'-vinylphenyl)-2H-benzotriazole is reported. The preponderance of quenching for both the monomer and excimer emissions is due to interception of the migrating excitation at the quencher site, although additional quenching results via long-range dipole-dipole energy transfer from the monomer and excimer traps to the quencher trap. The quenching of the monomer fluorescence and phosphorescence and that of the excimer fluorescence were found to be temperature independent over the ranges 14-58 and 191-296 K, respectively. Most significantly, it is concluded that the energy migration process is temperature independent over the range 14-296 K.

O'Connor, Donald B.↗

NASA NTRS1996

Synthesis of long Prebiotic Oligomers on Mineral Surfaces

Most theories of the origin of biological organization assume that polymers with lengths in the range of 30-60 monomers are needed to make a genetic system viable. But it has not proved possible to synthesize plausibly prebiotic polymers this long by condensation in aqueous solution, because hydrolysis competes with polymerization. The potential of mineral surfaces to facilitate prebiotic polymerization was pointed out long ago. Here we describe a system that models prebiotic polymerization by the oligomerization of activated monomers -both nucleotides and amino acids. We find that whereas the reactions in solution produce only short oligomers (the longest typically being a 10-mer), the presence of mineral surfaces (montmorillonite for nucleotides, illite and hydroxylapatite for amino adds) induces the formation of oligomers up to 55 monomers long. These are formed by successive "feedings" with the monomers; polymerization takes place on the mineral surfaces in a manner akin to solid-phase synthesis of biopolymers.

Ferris, James P.↗

NASA NTRS1999

New RTM/RI Resins for the HSCT

In the first portion of this work, 1,2,3,3,4,4-hexafluoro-1,2-bis[4-(dimethylhydroxysilyl)phenoxy]cyclobutane and 1,2,3,3,4,4-hexafluoro-1,2-bis[3-(dimethylhydroxysilyl)phenoxy]cyclobutane were prepared and homopolymerized to afford polymers with excellent thermal stability and Tgs of 27 C and -12 C, respectively. Despite the moderately high wt% of fluorin in the polymer structure (23.8%), these polymers had poor fuel resistance. In fact, swelling measurements indicate that these polymers had apparent solubility parameters of about 18.2 J (exp 1/2) m (exp -3/2) (toluene). Copolymerization of the disilanol monomers with fluorosilicone monomers afforded copolymers containing 20-30 wt% of the perfluorocyclobutane-containing structure displayed adequate fuel resistance, enhanced thermal stability, and a Tg low enough to meet the requirements of a High Speed Civil Transport (HSCT) fuel tank sealant. In the second part of this work, trifluorovinylether-terminated oligomers were prepared and polymerized via cyclodimerization. Initially, an alpha, omega-silanol-terminated fluorosilicone was endcapped with trifluorovinylether end groups via a two-step synthetic sequence. The oligomer was thermally cyclodimerized to a polymer that displayed thermal stability similar to that of a fluorosilicone homopolymer. Second, 1,3-bis[4-trifluorovinyl(oxy)phenyl]-1,3-(3,3,3-trifluoropropyl)dimethyldisiloxane and 1,3-bis{3-trifluorovinyl(oxy)phenyl]-1,3-(3,3,3-trifluoropropyl)dimethyldisiloxane were prepared and cyclodimerized to afford polymers that contained pendant trifluoropropyl groups. The pendant trifluoropropyl groups did enhance solvent resistance in aliphatic hydrocarbon solvents, however, no improvement was observed in aromatic hydrocarbon solvents. These polymers also displayed excellent thermal stability. In the last part of this work, a series of monomers was prepared by the DCC-promoted esterification of 4-[trifluorovinyl(oxy)benzoic acid with alpha, omega-functionalized hydrogenated and partially fluorinated alcohols. The monomers were cyclodimerized to the corresponding polymers. The polymers that did not contain beta hydrogens displayed significantly higher thermal stability than the fully hydrogenated polymers. A commercially-available alpha,omega-hydroxy-terminated perfluoropolyether was then functionalized with 4-[trifluorovinyl(oxy)benzoylchloride. An attempt was made to polymerize the resulting oligomer via the cyclodimerization of the terminal trifluorovinylether moieties. Although the viscosity of the oligomer increased significantly during polymerization, Gel Permeation Chromatography (GPC) analysis revealed that the Tetrahydrofuran (THF) soluble portion of the polymer did not have high molecular weight.

Harris, Frank W.↗