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At least 19 records

A study of the UV and VUV degradation of FEP

UV and VUV degradation of fluorinated ethylene propylene (FEP) copolymer was studied using electron spin resonance (ESR) spectroscopy, x-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM). The ESR study revealed the formation of a terminal polymer radical. The stability of this radical was investigated under different environments. An XPS study of FEP film exposed to VUV and atomic oxygen showed that oxidation takes place on the polymer surface. The study revealed also that the percentage of CF2 in the polymer surface decreased with exposure time and the percentage of CF, CF3, and carbon attached to oxygen increased. SEM micrographs of FEP film exposed to VUV and atomic oxygen identified a rough surface with undulations similar to sand dunes.

George, Graeme A.↗

Stable polymeric carbon radicals. Part 2: Attempts at the preparation of polyradicals of the triphenylmethyl type linked by P-phenylene units

As starting materials for the preparation of polyradicals of triphenylmethyl type linked by p-phenylene units bis(4-iodophenylmethane) and bis(4-iodo-2,5-dimethyl-phenylmethane) were synthesized by a Sandmeyer reaction from the corresponding diamino compounds and subsequently transformed into the corresponding polymeric hydrocarbons 6a and 6b by an Ullmann condensation. In the following step 6a and 6b were brominated at the tert. carbon atom by means of N-bromosuccinimide. The reaction of the resulting poly (4,4'-biphenylylen-alpha-bromobenzylidene)s (7a and 7b) with mercury afforded the corresponding radicals, the ESR spectra of which were recorded. From the methyl substituted polymer 7b poly (2,2'5,5-tetramethyl-4,4'-bi-phenylylen)phenylmethylidyne was formed, whereas the unsubstituted product 7a was transformed into a para-quinoide polymer with radical properties.

Braun, D.↗

ESR Measurement Of Crystallinity In Semicrystalline Polymers

Photogenerated free radicals decay at different rates in crystalline and amorphous phases. Degree of crystallinity in polymer having both crystalline and amorphous phases measured indirectly by technique based in part on electron-spin-resonance (ESR) spectroscopy. Accuracy of crystallinity determined by new technique equals or exceeds similar determinations by differential scanning calorimetry, wide-angle x-ray scattering, or measurement of density.

Kim, Soon Sam↗

Mechanisms of polymer degradation using an oxygen plasma generator

An RF oxygen plasma generator was used to produce polymer degradation which appears to be similar to that which has been observed in low Earth orbit. Mechanisms of this type of degradation were studied by collecting the reaction products in a cryogenic trap and identifying the molecular species using infrared, mass spectral, and X-ray diffraction techniques. No structurally dependent species were found from Kapton, Teflon, or Saran polymers. However, very reactive free radical entities are produced during the polymer degradation, as well as carbon dioxide and water. Reactions of the free radicals with the glass reaction vessel, with copper metal in the cold trap, and with a triphenyl phosphate scavenger in the cold trap, demonstrated the reactivity of the primary products.

Colony, Joe A.↗

Method of making a membrane having hydrophilic and hydrophobic surfaces for adhering cells or antibodies by using atomic oxygen or hydroxyl radicals

A portion of an organic polymer article such as a membrane is made hydrophilic by exposing a hydrophobic surface of the article to a depth of about 50 to about 5000 angstroms to atomic oxygen or hydroxyl radicals at a temperature below 100C., preferably below 40 C, to form a hydrophilic uniform surface layer of hydrophilic hydroxyl groups. The atomic oxygen and hydroxyl radicals are generated by a flowing afterglow microwave discharge, and the surface is outside of a plasma produced by the discharge. A membrane having both hydrophilic and hydrophobic surfaces can be used in an immunoassay by adhering antibodies to the hydrophobic surface. In another embodiment, the membrane is used in cell culturing where cells adhere to the hydrophilic surface. Prior to adhering cells, the hydrophilic surface may be grafted with a compatibilizing compound. A plurality of hydrophilic regions bounded by adjacent hydrophobic regions can be produced such that a maximum of one cell per each hydrophilic region adheres.

Koontz, Steven L.↗

Polymerization Initiated at the Sidewalls of Carbon Nanotubes

A process has been developed for growing polymer chains via anionic, cationic, or radical polymerization from the side walls of functionalized carbon nanotubes, which will facilitate greater dispersion in polymer matrices, and will greatly enhance reinforcement ability in polymeric material.

Tour, James M.↗

Electron spin resonance of gamma-irradiated poly/ethylene 2,6-naphthalene dicarboxylate/.

Study of the ESR spectra of this gamma-irradiated compound (PEN-2,6) aimed at determining the effect of replacing the phenylene ring with naphthalene rings in the polymer on the formation of radicals and at identifying the radical species. The two types of radicals trapped in the PEN-2,6 compound have been identified as -O-CH-CH2-O- (radical I) and a radical located on the naphthalene ring (radical II).

Rogowski, R. S.↗

In situ CF3 Detection in Low Pressure Inductive Discharges by Fourier Transform Infrared Spectroscopy

The detection of CF(x) (x=1-3) radicals in low pressure discharges using source gases such as CF4 and CHF3 is of importance to the understanding of their chemical structure and relevance in plasma based etching processes. These radicals are known to contribute to the formation of fluorocarbon polymer films, which affect the selectivity and anisotropy of etching. In this study, we present preliminary results of the quantitative measurement of trifluoromethyl radicals, CF3, in low pressure discharges. The discharge studied here is an inductively (transformer) coupled plasma (ICP) source in the GEC reference cell, operating on pure CF4 at pressures ranging from 10 - 100 mTorr, This plasma source generates higher electron number densities at lower operating pressures than obtainable with the parallel-plate capacitively coupled version of the GEC reference cell. Also, this expanded operating regime is more relevant to new generations of industrial plasma reactors being used by the microelectronics industry. Fourier transform infrared (FTIR) spectroscopy is employed to observe the absorption band of CF3 radicals in the electronic ground state X2Al in the region of 1233-1270/cm. The spectrometer is equipped with a high sensitivity HgCdTe (MCT) detector and has a fixed resolution of 0.125/cm. The CF3 concentrations are measured for a range of operating pressures and discharge power levels.

Kim, J. S.↗

Containerless polymeric microsphere production for biomedical applications

A containerless method that produces highly uniform microspheres (greater than 50 microns in diameter) from many materials has been developed for biomedical applications. A piezoelectrically vibrated drop generator forms uniform (monodisperse) monomer droplets that are either electrostatistically levitated and polymerized using UV irradiation, or free-radical polymerized. Spheres of 2-hydroxyethyl methacrylate polymer have been produced with diameters of 155 microns + or - 1.57 percent.

Rhim, W. K.↗

Solventless, curable fluid oligomeric systems for high performance microwave, acoustical and mechanical applications

While establishing the basis for a 'Technology 2000' product plan several years ago we plugged in the usual factors contributing toward product success: price/performance justifiable; profitable, warranting high quality maintenance, enhancement, and specific property improvement; narrow inventory requirements; and raw material integrable backwards with easily variable properties (molecular weight, functionality, and isomer control). We resolved this by selecting radical functional, low molecular weight polybutadiene liquid polymers. Encouraged by the need for solid rocket binders, several companies embarked on various perceptions of binder performance requirements over four decades ago. Initially dominated by progress of liquid polysulfides, soon a few settled primarily upon polybutadiene based binders. Such an approach in a few instances was exploited quite viably with a series of functional group terminated liquid polybutadienes: hydroxyl, mercaptan, carboxyl, vinyl, and amine. Good results are obtained for oligomers, liquid polymers, and their hybrids. The only significant limits on compounded products has been solvent resistance and oxidative sensitivity, unless sufficient proportion of sulfide or nitrile moiety is incorporated. For convenience, they have been grouped under the trademarks Nylane, Seamax, Oligomax, and Castomax.

Lefave, G. M.↗

Flame Suppression Agent, System and Uses

Aqueous droplets encapsulated in a flame retardant polymer are useful in suppressing combustion. Upon exposure to a flame, the encapsulated aqueous droplets rupture and vaporize, removing heat and displacing oxygen to retard the combustion process. The polymer encapsulant, through decomposition, may further add free radicals to the combustion atmosphere, thereby further retarding the combustion process. The encapsulated aqueous droplets may be used as a replacement to halon, water mist and dry powder flame suppression systems.

Parrish, Clyde F.↗

Method of cross-linking polyvinyl alcohol and other water soluble resins

A self supporting sheet structure comprising a water soluble, noncrosslinked polymer such as polyvinyl alcohol which is capable of being crosslinked by reaction with hydrogen atom radicals and hydroxyl molecule radicals is contacted with an aqueous solution having a pH of less than 8 and containing a dissolved salt in an amount sufficient to prevent substantial dissolution of the noncrosslinked polymer in the aqueous solution. The aqueous solution is then irradiated with ionizing radiation to form hydrogen atom radicals and hydroxyl molecule radicals and the irradiation is continued for a time sufficient to effect crosslinking of the water soluble polymer to produce a water insoluble polymer sheet structure. The method has particular application in the production of battery separators and electrode envelopes for alkaline batteries.

Phillipp, W. H.↗

Thermal rearrangements of unsaturated polymers

Thermal anaerobic uncatalyzed cyclizations and cis-trans isomerizations observed in unsaturated hydrocarbon polymers are surveyed. Three main types of cyclizations are described. Type I is a radical reaction which is caused by chain rupture and gives rise to six-membered rings; this reaction occurs during pyrolysis of polymers with double bonds in a 1,5- or 1,6-diene configuration. Type II is a (2 + 2) thermal cycloaddition of double bonds in certain polymers with a 1,6-diene structure; bicycloheptane structures result. Type III is an intramolecular ene reaction. Many polymers containing a double bond linking CH units display thermal cis-trans isomerization. The common activation energy is approximately 130 kJ/mol, and the initial rate constants are lower, for homologous polymers, the greater the separation of the carbon-carbon double bonds.

Golub, M. A.↗

Search for Extraterrestrial Origin of Atmospheric Trace Molecules Radio Sub-MM Observations During The Leonids

HCN is a minor constituent of the Earth atmosphere, with a typical volume mixing ratio around 10(exp -10) HCN per air molecule. At present, the main source of HCN in the lower atmosphere is expected to be biomass burning. The atmospheric HCN has been observed since 1981, first in the infrared, then at microwave radio frequencies. Globally, above 30 km, HCN measurements are in excess of model predictions based on standard photochemistry and biomass burning as the only HCN source. This excess has been explained by: 1) ion-catalyzed reactions in the entire stratosphere, involving CH.3CN as a precursor and/or 2) a high altitude source as a result of chemical production from the methyl radical CH3, or from injection or production by meteors. HCN is a minor constituent of cometary ices. HCN polymers or copolymers have been suggested as constituents of cometary refractory organic matter, and would thus be present in the incoming meteoroids, if these polymers survived their stay in interplanetary space after ejection. HCN may also be created from the CN radical decomposition product of organic carbon, after reaction with hydrogen-bearing molecules. To test the hypothesis of HCN input by meteoroids or the formation in the upper atmosphere from meteoric ablation products, we decided to monitor the HCN submillimeter lines around a major shower: the Leonids.

Depois, D.↗

Fire-Retardant Polymeric Additives

Polyhydroxyamide (PHA) and polymethoxyamide (PMeOA) are fire-retardant (FR) thermoplastic polymers and have been found to be useful as an additive for imparting fire retardant properties to other compatible, thermoplastic polymers (including some elastomers). Examples of compatible flammable polymers include nylons, polyesters, and acrylics. Unlike most prior additives, PHA and PMeOA do not appreciably degrade the mechanical properties of the matrix polymer; indeed, in some cases, mechanical properties are enhanced. Also, unlike some prior additives, PHA and PMeOA do not decompose into large amounts of corrosive or toxic compounds during combustion and can be processed at elevated temperatures. PMeOA derivative formulations were synthesized and used as an FR additive in the fabrication of polyamide (PA) and polystyrene (PS) composites with notable reduction (>30 percent for PS) in peak heat release rates compared to the neat polymer as measured by a Cone Calorimeter (ASTM E1354). Synergistic effects were noted with nanosilica composites. These nanosilica composites had more than 50-percent reduction in peak heat release rates. In a typical application, a flammable thermoplastic, thermoplastic blend, or elastomer that one seeks to render flame-retardant is first dry-mixed with PHA or PMeOA or derivative thereof. The proportion of PHA or PMeOA or derivative in the mixture is typically chosen to lie between 1 and 20 weight percent. The dry blend can then be melt-extruded. The extruded polymer blend can further be extruded and/or molded into fibers, pipes, or any other of a variety of objects that may be required to be fire-retardant. The physical and chemical mechanisms which impart flame retardancy of the additive include inhibiting free-radical oxidation in the vapor phase, preventing vaporization of fuel (the polymer), and cooling through the formation of chemical bonds in either the vapor or the condensed phase. Under thermal stress, the cyclic hydroxyl/ methoxy component forms polybenzoxazole (PBO) in a reaction that absorbs heat from its surroundings. PBO under thermal stress cross-links, forming a protective char layer, which thermally insulates the polymer. Thus, the formation of the char layer further assists to extinguish the fire by preventing vaporization of the polymeric fuel.

Williams, Martha K.↗