A calculation of thermal degradation initiated by random scission, unsteady radical concentration
β Scribed by Atsushi Inaba; Takashi Kashiwagi
- Book ID
- 103073579
- Publisher
- Elsevier Science
- Year
- 1987
- Tongue
- English
- Weight
- 927 KB
- Volume
- 23
- Category
- Article
- ISSN
- 0014-3057
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β¦ Synopsis
Abstraet~hanges in molecular weight distribution and in sample volume were calculated for thermal degradation of a polymer. The thermal degradation scheme consists of random scission initiation, depropagation and disproportionation termination reactions. An unsteady radical concentration was considered. There are two parameters, normalized zip length z/x o and radical number per initial chain length z'x 0, describing the thermal degradation scheme with an unsteady radical concentration. The effects of the initial number-average molecular weight and order of the disproportionation termination reaction on changes in molecular weight, the sample volume and polydispersity are not significant as long as these two parameters have the same value for each polymer sample. Molecular weights of a degrading sample calculated from the steady state radical concentration tend to be over-estimated and sample volumes tend to be underestimated compared to those calculated with an unsteady radical concentration. The validity of approximations used in the calculation assuming a steady state radical concentration is examined by comparing with results calculated with an unsteady radical concentration for various values of the two parameters. An unrealistically large build-up of monomer radicals is found for both calculations based on the steady state and the unsteady radical concentrations. Two special treatments of monomer radicals can dissipate the build-up of monomer radicals: (1) their immediate vaporization, or (2) an enhanced rate of the termination reaction for the monomer radicals. As a guide, the model based on an unsteady radical concentration is preferred, if the value of z'x0 exceeds 0.1.
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