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A novel method was developed for the sampling of volatiles produces bypolymer decomposition during UL94 standard flammability tests, allowing tocollect, separate and analyze the precise composition of the fuel mixturefeeding the flame in the real flammability tests. The system was validated onepoxy resin/polyhedral oligomeric silsesquioxanes and found extremelyinformative for the understanding of the flame retardancy mechanisms of POSS,previously referred to as the blowing-out effect. Collected products wereanalyzed by infrared spectroscopy and gas chromatography/mass spectroscopy, toidentify the gaseous and liquid decomposition products, allowing to depict acomprehensive decomposition pathway for the epoxy resin. Lightweight volatiles,gaseous at room temperature, showed limited differences as a function ofDOPO-POSS, whereas mixtures of liquid products evidenced for dramatic changesin the relative concentration as a function of DOPO-POSS. In pristine epoxyresin, the most abundant products were recognized as benzene, phenol,naphthalene and toluene, along with several tens of other aromatic productsobserved in lower amounts. The presence of DOPO-POSS at low concentrationradically changes the composition of the aromatic volatiles mixture, as nosignificant amount of benzene is produced, while phenol becomes the mainproduct, accounting for about half of the total, isopropyl phenol and bisphenolA, along with several tens of other products in lower concentrations. Suchmodification of the fuel mixture feeding the flame provided an explanation forthe lower flammability of this formulation, as well as for the phenomenology ofthe blowing out effect.

FTIR and GCMS analysis of epoxy resin decomposition products feeding the  flame during UL 94 standard flammability test. Application to the  understanding of the blowing-out effect in epoxy/polyhedral silsesquioxane  formulations