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  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 967-985 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The transport of oxygen by diffusion from the environment into a gas stream was investigated as a model for the analogous process in a diffusion flame. The amount transported at steady-state conditions depended on the flow rate, diameter, and spatial orientation of the gas stream. A change of the same extrinsic parameters in a diffusion flame caused changes of burner surface temperature, maximum flame temperature, and flame height. These responses were correlated and yielded an overall activation energy of the rate-controlling reaction step in the combustion process equal to 49 kcal/mole. This value was the same for several types of diffusion flames examined and appeared to be associated with the CO/CO2 conversion process at the high-temperature flame boundary. Flame quenching was demonstrated to occur at a minimum fuel flow rate and minimum environmental oxygen concentration which were characteristic for a given fuel. Quenching conditions were related to the diffusion rate of oxygen into the product effluent stream. Quenching of a polymer flame by depletion of environmental oxygen was governed by the same processes. The effect of extrinsic parameters on polymer flames is discussed in Part II.
    Additional Material: 16 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 585-621 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Experimental conditions have been defined for the steady-state combustion of vertically positioned polymer rods burning at the top surface. Temperature and composition profiles through solid and gas phases of the system, polymer consumption rate, and flame height were measured, and the response of these parameters to changes of the oxygen concentration in the environment were determined. Measurements showed that unreacted oxygen diffused from the environment to the burning surface and was absorbed into the polymer, forming a well defined oxygen-rich layer. Concentration of chemically bound oxygen at the surface of this layer were high, e.g., with polypropylene ca. 26 wt-%, and identical with the stoichiometry of the gases leaving the surface and serving as fuel for the flame. The composition of the gas phase at the surface indicated the conversion of 11.4% of the hydrocarbon fuel to CO, CO2, and H2O. An energy balance for the system confirmed that fuel production in this surface layer takes place via simultaneous oxidative and pyrolytic degradation of the polymer, with exothermic processes supplying the energy for endothermic processes. Conductive and radiative contributions from the gas phase were found to play a minor role in maintaining fuel formation. The rate of degradation of a polymer to fuel, normalized to the area of the burning surface, was found to be independent of polymer supply rate and to increase with the oxygen concentration in the environment. The degradation process was successfully modeled in TGA experiments at temperatures and oxygen concentrations representative of the burning surface. The existence of an oxidative surface layer was confirmed and the TGA degradation rate related to the surface-to-volume ratio of the polymer sample. Compositional analysis of a methane diffusion flame of a geometry identical to that of the polymer flame, revealed the presence of unreacted oxygen throughout the preheating zone and at the surface of the burner. Conversion of fuel to final combustion products at the surface was 6.3%. Temperature and composition changes as a function of oxygen concentration in the environment were determined and compared with the polymer diffusion flame. It was concluded that a polymer flame, because of its autogenerative fuel production, possesses only one degree of freedom, viz., the oxygen concentration in the environment, in contrast to the conventionally fueled diffusion flame for which fuel supply rate is an additional independent parameter. Due to this single degree of freedom, the sensitivity of the polymer flame to environmental influences is increased. Effects caused by these extrinsic factors will be the subject of a separate report.
    Additional Material: 20 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 987-1009 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The responses of a polymer flame to changes of specimen diameter, ignition position, and stability of the burning surface were determined. These extrinsic flame parameters restricted the transport of oxygen from the environment to the burning surface. With increasing restriction the oxygen demand from the environment for self-sustained combustion increased from a minimum oxygen demand at maximum access of environmental oxygen to the burning surface. This increase in oxygen demand was measured and correlated with surface oxygen concentrations estimated from the diffusion data of Part I. The minimum oxygen demand was demonstrated as characteristic for a given polymer and intrinsic in its chemical structure. This minimum oxygen demand, termed intrinsic combustibility, has been correlated with a polymer's thermooxidative stability, measured by thermogravimetric analysis at specific conditions. An intrinsic combustibility scale for polymers is given. In contrast, polymer flammability, as commonly measured in air, is interpreted as a variable property that depends on the extent of the interaction between extrinsic parameters, which are set by the testing configuration, with intrinsic combustibility.
    Additional Material: 13 Ill.
    Type of Medium: Electronic Resource
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