Abstract: | The thermal oxidation of poly(bismaleimide) of the F655‐2 type, supplied by Hexcel‐Genin, was studied by isothermal gravimetry at 180, 210, and 240°C and various oxygen pressures ranging from 0 to 1.2 bar. Comparison of various sample thicknesses and visible microscopy observations on bulk aged samples shows that the whole oxidized layer has a depth of about 75 μm at 240°C, 138 μm at 210°C, and 229 μm at 180°C. An attempt was made to build a kinetic model to predict this depth. It is based on a differential equation in which O2 diffusion and its consumption rate, r(C), are coupled, C being the O2 concentration. Its resolution needs two sets of experiments: the first one to determine the O2 diffusivity and solubility in the polymer, and the second one to determine r(C). The mathematical form of r(C) is derived from a mechanistic scheme of radical chain oxidation in which initiation is mainly due to POOH decomposition. This expression contains two kinetic parameters, α and β, the values of which are determined from the experimental curves of mass loss rate against O2 pressure (in the stationary state). The theoretical predictions, at each temperature under consideration, are in excellent agreement with experimental results. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 3418–3430, 2001 |