Oxidative Decomposition of Poly(phenylene sulfide) Composites Under Fast Elevation of Temperature.

The thermal resistance of carbon fiber-reinforced poly(phenylene sulfide) to harsh oxidative conditions is investigated through thermogravimetric experiments performed in an oxygen atmosphere. While these materials usually show great resistance against thermal decomposition in a nitrogen atmosphere, the experiments in oxygen reveal the total decomposition of both the matrix and the carbon fibers. The Gram-Schmidt signal, obtained by coupling thermogravimetric analysis in standard conditions with Fourier-transform infrared spectroscopy, exhibits multiple events, evidencing that the decomposition proceeds through distinct stages. The first step characterizes the char formation, while the second relates to its oxidative decomposition. A third step, only observed for composites, is interpreted as the signature of the oxidative decomposition of carbon fibers. To mimic the sudden elevation of temperature encountered during a fire, the analyses are performed at rates of up to 500 K min^-1. These specific experimental conditions reveal a complex dependence of the thermogravimetric signature on the heating rate. Independent of the atmosphere, nitrogen or oxygen, the characteristic temperature of decomposition follows a bell-shape trend, resulting from the combination of lag effects and thermal-conductivity limitations. Additionally, the increase of the heating rate causes the Gram-Schmidt signal to evolve toward a broad peak with indistinct events. To investigate whether these changes affect the decomposition products, the infrared spectra, continuously recorded to probe the whole decomposition, are compared with those from the database. The char formation is characterized by the production of sulfur dioxide, while carbon dioxide is the main product emitted during both char and fiber oxidative decomposition. Owing to the merging of the decomposition stages, sulfur-dioxide detection is partly supplanted by that of carbon dioxide under fast elevations of temperature.