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The Role of Decomposition Kinetics in Pyrolysis Modeling - Application to a Fire Retardant Polyester Composite

Lautenberger, C., Kim, E., Dembsey, N.A. and Fernandez-Pello, A.C., 2008. The Role of Decomposition Kinetics in Pyrolysis Modeling - Application to a Fire Retardant Polyester Composite. Fire Safety Science 9: 1201-1212. doi:10.3801/IAFSS.FSS.9-1201


This work assesses the effect of decomposition kinetics on overall pyrolysis behavior using experimental data from thermogravimetric analysis (TGA) and Fire Propagation Apparatus (FPA) experiments. TGA data are presented for an unsaturated brominated polyester resin (reinforcement free), and the FPA is used to investigate the pyrolysis behavior of a fiber reinforced polymer (FRP) composite slab with matrix comprised of the same resin tested via TGA. Three different kinetic models are fit to the TGA data: singlestep nth order, 3-step nth order, and 3-step nth order with one autocatalytic step. These kinetics models are then used to simulate the pyrolysis of a composite slab in the FPA, with thermophysical properties estimated by genetic algorithm optimization. It is shown that the two 3-step mechanisms provide nearly identical calculations of total mass loss rate (MLR) in the FPA, while the single-step mechanism provides similar, but quantitatively different, MLR predictions. Although no broad conclusions regarding the importance of multi-step thermal decomposition kinetics can be drawn on the basis of a single study, detailed reaction mechanisms may be superfluous unless TGA curves show multiple distinct reaction peaks and/or all thermophysical properties/model input parameters are precisely known.

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