Multi-scale and multi-technical analysis of the thermal degradation of poly(ether imide)

The thermal degradation of PEI has been studied in wide ranges of temperature (between 180 and 250 °C) and oxygen partial pressure (between 0.21 and 50 bars). On one hand, the chemical ageing mechanisms have been analysed and elucidated by FTIR spectrophotometry and by differential calorimetry (DSC) on sufficiently thin PEI films (between 10 and 60 μm thickness) to be totally free of the effects of oxygen diffusion. As expected, and by analogy with other aromatic polymers of similar chemical structure, oxidation occurs preferentially on the methyl groups of the isopropylidene unit of the bisphenol A part, thus causing the disappearance of their characteristic IR absorption band at 2970 cm−1 and the growth of a new IR absorption band at 3350 cm−1, attributed to alcohols. In addition, oxidation leads successively to a relative predominance of chain scissions and crosslinking, resulting in a non-monotonic change of Tg. On the other hand, the consequences of oxidation on the elastic properties have been analysed and elucidated by micro-indentation on polished cross-sections of PEI plates of 3 mm thickness. The diffusion control of oxidation leads to the development of profiles of Young's modulus within the sample thickness, which correlate perfectly with the changes in chemical structure determined by FTIR spectrophotometry. However, the increase in Young's modulus in the superficial oxidized layer is not the direct consequence of oxidation but of a physical ageing.