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Degradation of polymeric insulators may be significantly reduced when polymer surfaces are coated with film having gradation of dielectric constants, larger where it is in contact with polymer and smaller at its exposed surface.
Process produces small spherical polymeric particles which have polycations bound to them. In emulsion form, particles present large positively charged surface which is available to absorb polyanions. This properly can be used in removing heparin from blood or bile acids from the digestive tract. Other anions, such as DNA and RNA, can also be removed from aqueous solutions.
A procedure has been developed whereby nitrogen can be incorporated into an organic film from an ethylene-nitrogen gas mixture using an internal electrode capacitively coupled radio frequency reactor. The presence of nitrogen has been shown directly by infrared transmittance spectra and electron spectroscopic chemical analysis data, and further indirect evidence was provided by dielectric measurements and by the reverse osmosis properties of the film. Preparation of a nitrogen containing film did not require vapor from an organic nitrogen containing liquid monomer. Some control over the bonding and stoichiometry of the polymer film was provided by the added degree of freedom of the nitrogen partial pressure in the gas mixture. This new parameter strongly affected the dielectric properties of the plasma polymerized film and could affect the reverse osmosis behavior.
The need for protective coatings on critical optical surfaces, such as halide crystal windows or lenses used in spectroscopy, has long been recognized. It has been demonstrated that thin, one micron, organic coatings produced by polymerization of flourinated monomers in low temperature gas discharge (plasma) exhibit very high degrees of moisture resistence, e.g., hundreds of hours protection for cesium iodide vs. minutes before degradation sets in for untreated surfaces. The index of refraction of these coatings is intermediate between that of the halide substrate and air, a condition for anti-reflection, another desirable property of optical coatings. Thus, the organic coatings not only offer protection, but improved transmittance as well. The polymer coating is non-absorbing over the range 0.4 to 40 microns with an exception at 8.0 microns, the expected absorption for C-F bonds.
A free oscillation torsion pendulum is described, which has been designed to measure accurately the dynamic shear modulus and logarithmic decrement of polymeric thin films and fibers, at frequencies of 0.1 to 10 Hz and a temperature range of 4.2 to 450 K. The instrument can also provide in situ tensile deformations of up to 5%. The specimen geometry necessary to obtain reliable modulus measurements with thin films is discussed, and typical data are presented which exhibit hitherto unreported relaxation processes, discernible by this instrument.
Thirty-nine samples of polymeric materials were evaluated to determine the apparent lethal concentrations of their pyrolysis products. The materials were compared on the basis of the apparent lethal concentration for 50 percent of the test animals. Relative toxicity rankings based o apparent lethal concentration values can differ significantly depending on whether they are based on weight of sample charged or weight of sample pyrolyzed. The ranking of polyphenylene sulfide is particularly sensitive to this difference.
Relative toxicity data for a large number of natural and synthetic polymeric materials are presented which were obtained by 11 pyrolysis and three flaming-combustion test methods. The materials tested include flexible and rigid polyurethane foams, different kinds of fabrics and woods, and a variety of commodity polymers such as polyethylene. Animal exposure chambers of different volumes containing mice, rats, or rabbits were used in the tests, which were performed over the temperature range from ambient to 800 C with and without air flow or recirculation. The test results are found to be sensitive to such variables as exposure mode, temperature, air flow and dilution, material concentration, and animal species, but relative toxicity rankings appear to be similar for many methods and materials. It is concluded that times to incapacitance and to death provide a more suitable basis for relative toxicity rankings than percent mortality alone, that temperature is the most important variable in the tests reported, and that variables such as chamber volume and animal species may not significantly affect the rankings.
Plasma polymerized vinyltrimethoxy silane films were deposited on transparent polycarbonate substrates. The adherent, clear films protected the substrates from abrasion and also served as antireflection coatings. Posttreatment of the vinyltrimethoxy silane films in an oxygen glow discharge further improved the abrasion resistance. ESCA (electron spectroscopy for chemical analysis) and IR transmission spectra of some films were recorded, and an elemental analysis of the films was obtained.
Apparent lethal concentrations for 50 per cent of the test animals within a 30-min exposure period (ALC/50/) were determined for seventeen samples of polymeric materials, using the screening test method. The materials evaluated included resin-glass composites, film composites, and miscellaneous resins. ALC(50) values, based on weight of original sample charged, ranged from 24 to 110 mg/l. Modified phenolic resins seemed to exhibit less toxicity than the baseline epoxy resins. Among the film composites evaluated, only flame modified polyvinyl fluoride appeared to exhibit less toxicity than the baseline polyvinyl fluoride film.
Techniques are discussed for limiting or controlling the degradation products (outgassing) of polymeric materials in the space environment. One technique, now ASTM E-595-77, is used to screen out those materials which lose greater than 1% Total Mass Loss when in vacuum for 24 hours at 125 C and which have more than 0.10% Collected Volatile Condensable Materials condensing on a collector surface at 25 C. Examples of silicone materials which are high and low in outgassing are given. The numerous mechanical motions in spacecraft experiments require liquid lubricants which also might degrade in space. Labyrinth seals and barrier films are utilized to limit the degradation of or from these lubricants. A recoverable in-flight experiment has been proposed for making definitive measurements of how effective these techniques are in limiting the amounts and escape paths of outgassed molecules.
Four research and development areas are considered for further exploration in the quest of more flame-resistant polymeric materials. It is suggested that improvements in phenolphthalein polycarbonate processability may be gained through linear free energy relationship correlations. Looped functionality in the backbone of a polymer leads to both improved thermal resistance and increased solubility. The guidelines used in the pyrolytic carbon production constitute a good starting point for the development of improved flame-resistant materials. Numerous organic reactions requiring high temperatures and the techniques of protected functionality and latent functionality constitute the third area for exploration. Finally, some well-known organic reactions are suggested for the formation of polymers that were not made before.
A plasma polymerization process for the deposition of a dielectric polymer coating on a substrate comprising disposing of the substrate in a closed reactor between two temperature controlled electrodes connected to a power supply is presented. A vacuum is maintained within the closed reactor, causing a monomer gas or gas mixture of a monomer and diluent to flow into the reactor, generating a plasma between the electrodes. The vacuum varies and controls the dielectric constant of the polymer coating being deposited by regulating the gas total and partial pressure, the electric field strength and frequency, and the current density.
The nonenzymatic, nontemplate catalysis of nucleotide polymerization by Pb(2+) ions, a possible prebiotic catalyst, is reported. Adenosine and uridine phosphoimidazoles were reacted in buffered solutions of lead salts and products were analyzed by means of paper chromatography and electrophoresis. In the presence of Pb(2+) ion at pH 8.0 and 7.0 the reaction is found to progress rapidly with excellent yields of oligomers, with optimal yields observed at pH 8.0. Little temperature dependence in the range 0 to 30 C is observed, however hydrolysis of the reaction products is minimal when the reaction is carried out at 0 C. Results show that the yield of oligomers is insensitive to mixing or the source of lead ions, indicating that naturally occurring minerals or precipitates could be a source of Pb(2+) ions under prebiotic conditions.
Various polymeric materials, including synthetic polymers and cellulosic materials, were evaluated at different temperatures, heating rates and air flow rates for thermophysical and toxicological responses. It is shown that char yields appeared to be a function of air access as much as of the chemical structure of the material. It is stated that the sensitivity of the apparent thermal stability of some materials to air access is so marked that thermogravimetric studies in oxygen-free atmospheres may be a consistently misleading approach to comparing synthetic polymers intended to increase fire safety. Toxicity also appeared to be a function of temperature and air access as much as of the chemical structure of the material. Toxicity of the gases evolved seemed to increase with increasing char yield for some polymers.
The polymerization of ethylene in an atmospheric pressure-pulsed discharge has been studied. Partial pressures of ethylene up to 4 kN/sq m were used with helium as a diluent. Deposition rates (on glass slides) were the same throughout the discharge volume over a wide range of operating conditions. These rates were in the 1-2 A/sec range. The films were clear, soft, and showed good adhesion to the glass substrates. Oligomers large enough to visibly scatter 637.8-nm light were observed in the gas phase under all conditions in which film deposition occurred. The experimental results suggest that Brownian diffusion of these oligomers was the rate-limiting step in the film deposition process.
Various polymeric materials were evaluated at different temperatures for relative flammability as defined by the HC value, a measure of the concentration of combustibles related to the concentration representing the lower limit of flammability. Flammability generally decreased with increasing char yield. This appears to support the hypothesis that increasing char yield decreases flammability by reducing the probability of reaching the lower flammable limits.
The object to be coated was placed in a reaction area located in a luminescent discharge chamber. By introducing the polymerizable material in this reaction area and applying an electrical field to this reaction, a polymerized film was obtained on the coating object under controlled conditions. By the use of thermomechanical treatment on the object, the undesirable effects of discoloration, brittleness, and viscosity can be controlled.
Glass slides were coated with plasma-polymerized tetrafluoroethylene films of different thickness using the glow discharge technique in a tube-shaped chamber, and the plasma conditions, film growth rates, light permeability of the polymer films, and particle bond strength in the polymer films were studied. Ashed sections of mouse organs and ashed bacillus spores were also coated to give them hydrophobic treatment without damaging their shapes or appearance. The hydrophobic coating of the specimens was successful, and the fine ash patterns were strongly fixed onto the glass slides, making permanent preparations.