Abstract
Product ratios, fractional conversions, and rates of pyrolysis may show confusing variations with sample size or thickness. There are several reasons for this, amongst which heat transfer and temperature gradients across the sample are important. To obtain meaningful results, a suitable approach is to reduce sample size to find a sample thickness range over which the reaction parameters are independent of the size. The objective in this approach is thereby to eliminate any effects of sample size. Recent work however has shown that investigations of the dependence of reaction parameters on sample size may reveal mechanistic features of the pyrolysis process itself. Two such features are: (a) secondary reactions which occur during the residence time of primary products in the melt, and (b) diffusion-restriction of the interaction of long-chain radicals, when the thickness of the degrading film is comparable with the diameter of the hydrodynamic volume of the polymer molecules. Both types of study have been performed on a range of polystyrene and PMMA samples.
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