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Thermal degradation of polyoxypropylene glycol- toluene 2, 4-diisocyanate polymer /POPG-TDI/ OCCURS by random scission of urethane linkages to regenerate hydroxyl and isocyanate
Polymer degradation to small fragments is treated as a rate controlling step in hybrid rocket combustion. Both numerical and approximate analytical solutions of the complete energy and polymer chain bond conservation equations for the condensed phase are obtained. Comparison with inert atmosphere data is very good. It is found that the intersect of curves of pyrolysis rate versus interface temperature for hybrid combustors, with the thermal degradation theory, falls at a pyrolysis rate very close to that for which a pressure dependence begins to be observable. Since simple thermal degradation cannot give sufficient depolymerization at higher pyrolysis rates, it is suggested that oxidative catalysis of the process occurs at the surface, giving a first order dependence on reactive species concentration at the wall. Estimates of the ratio of this activation energy and interface temperature are in agreement with best fit procedures for hybrid combustion data. Requisite active species concentrations and flux are shown to be compatible with turbulent transport. Pressure dependence of hybrid rocket fuel regression rate is thus shown to be describable in a consistent manner in terms of reactive species catalysis of polymer degradation.
Polymer degradation dosimeter of polyisobutylene in heptane noting viscosity range effects, concentration change and molecular weight
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.
Column elution fractionation and thermal degradation of polyoxypropylene glycol-toluene diisocyanate /PPG-TDI/ polymers of molecular weight of about 100,000
Polymer thermal degradation theory of pressure sensitive hybrid combustion, calculating linear regression rates
To test the hypothesis that exposure to ultrafine particles results in an increased interstiatilization of the particles which is accompanied by an acute pathological inflammation, rats were exposed to titanium dioxide (TiO2) particles by intratracheal instillation and by inhalation. Both acute intratracheal instillation and subchronic inhalation studies on rats show that ultrafine TiO2 particles access the pulmonary interstitium to a larger extent than fine particles and that they elicit an inflammatory response as indicated by PMN increase in lavaged cells. The release of ultrafine particles into the air of an enclosed environment from a thermodegradation event or from other sources is a potential hazard for astronauts. Knowing the mechanisms of action is a prerequisite for technical or medical countermeasures.
There is a need to simulate the near-Earth-orbit environmental conditions, and it is useful to be able to monitor the changes in physical properties of spacecraft materials. Two different methods for simulating the vacuum-ultraviolet (VUV) and soft X-ray near-Earth-orbit flux are presented. Also, methods for monitoring the changes in optical ultraviolet transmission and mass loss are presented. The results of exposures to VUV photons and charged particles on these materials are discussed.
Ultraviolet degradation of polymer films
Toxic gases evolved from the thermal oxidative degradation of synthetic or natural polymers in small laboratory chambers or in large scale fire tests are measured by several different analytical methods. Gas detector tubes are used for fast on-site detection of suspect toxic gases. The infrared spectroscopic method is an excellent qualitative and quantitative analysis for some toxic gases. Permanent gases such as carbon monoxide, carbon dioxide, methane and ethylene, can be quantitatively determined by gas chromatography. Highly toxic and corrosive gases such as nitrogen oxides, hydrogen cyanide, hydrogen fluoride, hydrogen chloride and sulfur dioxide should be passed into a scrubbing solution for subsequent analysis by either specific ion electrodes or spectrophotometric methods. Low-concentration toxic organic vapors can be concentrated in a cold trap and then analyzed by gas chromatography and mass spectrometry. The limitations of different methods are discussed.
Electron-spin-resonance (ESR) spectroscopy and Arrhenius plots used to determine maximum safe temperature for accelerated testing of photothermal degradation of polymers. Aging accelerated by increasing illumination, temperature, or both. Results of aging tests at temperatures higher than those encountered in normal use valid as long as mechanism of degradation same throughout range of temperatures. Transition between different mechanisms at some temperature identified via transition between activation energies, manifesting itself as change in slope of Arrhenius plot at that temperature.
The effects of cavitating flow on the polymeric additives used in functional fluids are described. A comparison of thermal and mechanical stability tests for these polymer solutions show distinct differences in the machanism of the polymer degradation. The thermal degradation tests appear to cause an unzippering or depolymerization type of reaction in which there is no particular selectivity based on molecular weight. The mechanical degradation of these fluids appears to be based on molecular weight. Measurements of molecular weight distributions during mechanical degradation show that for a given level of intensity only molecules above a certain minimum size are degraded. The effects of ultrasonic radiation on polymer degradation are reported. Tests were conducted to demonstrate the mechanism of mechanical polymer degradiation in an orifice. A more severe test than the orifice test in which two tapered roller bearings loaded against each other produce the mechanical breakdown is discussed.
Group of phthalocyanine polymers resist thermal degradation. Polymers expected semiconducting. Principal applications probably in molded or laminated parts that have to withstand high temperatures. Polymers made from either of two classes of monomer: Bisphthalonitriles with imide linkages or Bisphthalonitriles with ester-imide linkages.
Electron-spin resonance identifies polymer-degradation reactions and their kinetics. New technique enables derivation of kinetic model of specific chemical reactions involved in degradation of particular polymer. Detailed information provided by new method enables prediction of aging characteristics long before manifestation of macroscopic mechanical properties.
Vacuum ultraviolet (VUV) radiation of wavelengths between 115 and 200 nm produced by the Sun in the space environment can degrade polymer films, producing changes in their optical, mechanical, and chemical properties. These effects are particularly important for thin polymer films being considered for ultralightweight space structures, because, for most polymers, VUV radiation is absorbed in a thin surface layer. The NASA Glenn Research Center has developed facilities and methods for long-term ground testing of polymer films to evaluate space environmental VUV radiation effects. VUV exposure can also be used as part of combined or sequential simulated space environmental exposures to determine combined damaging effects with other aspects of the space environment, which include solar ultraviolet radiation, solar flare x-rays, electron and proton radiation, atomic oxygen (for low-Earth-orbit missions), and temperature effects. Because the wavelength sensitivity of VUV damage is not well known for most materials, Glenn's VUV facility uses a broad-spectrum deuterium lamp with a magnesium fluoride window that provides output between 115 and 200 nm. Deuterium lamps of this type were characterized by the National Institute of Standards and Technology and through measurements at Glenn. Spectral irradiance measurements show that from approximately 115 to 160 nm, deuterium lamp irradiance can be many times that of air mass zero solar irradiance, and as wavelength increases above approximately 160 nm, deuterium lamp irradiance decreases in comparison to the Sun. The facility is a cryopumped vacuum chamber that achieves a system pressure of approximately 5310(exp -6) torr. It contains four individual VUV-exposure compartments in vacuum, separated by water-cooled copper walls to minimize VUV radiation and any sample contamination cross interactions between compartments. Each VUV-exposure compartment contains a VUV deuterium lamp, a motor-controlled sample stage coupled with a moveable cesium iodide VUV phototube, and two thermocouples for temperature measurement. The vacuum chamber and exterior equipment is shown. Each VUV lamp is located at the top of the chamber with its projection-tube pushed through an O-ring compression fitting. The lamp assemblies are located on ports that can be isolated from the rest of the vacuum chamber, permitting maintenance or replacement of the lamps without breaking vacuum in the main chamber where the samples are located. A view of two of the four interior VUV-exposure compartments, including the moveable sample stages and detector holders is also shown. Glenn is using this facility to support testing of Next Generation Space Telescope sunshield materials that is being led by the NASA Goddard Space Flight Center and to develop an understanding of the wavelength, intensity, and temperature dependence of VUV-induced polymer degradation.
Chip polymer tantalum capacitors (CPTCs) are more sensitive to environments compared to conventional, MnO2 cathode capacitors. Contrary to MnO2 capacitors, CPTCs can degrade with time of storage even in dry conditions, that might limit their use for space applications. Performance of CPTCs depends on the amount of moisture in the slug, and varies with time of storage after manufacturing. For this reason, characteristics of the parts and qualification testing should be carried out after preconditioning to stabilize moisture content. This work analyzes kinetics of moisture sorption and desorption in different types of CPTCs from three manufacturers. Variations of capacitance, dissipation factor, ESR, and leakage currents caused by exposure to humid, dry, and radiation environments are discussed. Examples of the effects of long-term exposure to vacuum and humid environments at 85%RH are presented. Temperature dependencies of the characteristic times of moisture diffusion allow for assessments of the bake-out times that are necessary to avoid pop-corning failures after soldering and to precondition parts before qualification testing.
Degradation of hydrocarbon polymers by exposure to 275 F for 400 hours in presence and in absence of ammonium perchlorate
Technique for correlation of flight and ground tests of effects of ultraviolet radiation on polymer films