Polyimide degradation

In the absence of air and moisture, the polyimide degrades through a pyrolytic reaction. Since radical-initiated oxidation can be catalyzed by the presence of transition metals, the nature of the substrate will have a profound effect on the thermal life of the film in air. 

Fig. 1.7. Schematic mechanism of polyimide degradation the dashed lines show by-products of PI after UV exposure.

Journal of Polymers and the Environment 8, No.4, Oct. 2000, p. 167-74 SENSITIVE ELECTROCHEMICAL IMPEDANCE SPECTROSCOPY METHOD FOR DETECTION OF POLYIMIDE DEGRADATION BY... 

Polyamide or polyimide polymers are resistant to aliphatic, aromatic, and chlorinated or fluorinated hydrocarbons as well as to many acidic and basic systems but are degraded by high-temperature caustic exposures. 

As mentioned earlier, siloxanes impart a number of beneficial properties to polymeric systems into which they are incorporated, including enhanced solubility, resistance to degradation in aggressive oxygen environments, impact resistance and modified surface properties. These particular advantages render polysiloxane-modified polyimides attractive for aerospace, microelectronic and other high performance applications (40-43). 

The thermal stability of the polymer is an interesting criterion for one to develop because several authors have considered photoablation as proceeding through a purely thermal degradation. Polyimide and polyphenylquinoxaline, two polymers of the thermostable family, are stable up to a temperature of approximately 500. As seen in Figure 3a, they display quite... 

Interpretation of these curves show that Poly (vinyl chloride) (PVC) first loses HC1 later the mixture of unsaturated carbon-carbon backbone and unchanged poly (vinyl chloride) partly degrades to small fragments. Poly (methyl methacrylate) (PMMA), branched polyethylene (HPPE), and polytetrafluorethylene (PTFE) degrade completely to volatile fragments, while a polyimide (PI) partially decomposes, forming a char above 800°C. 

In comparison, no structural modification of model B was seen before 120 h of aging (80 °C). However, after 120 h two small doublets appeared in the NMR spectrum and several additional peaks became noticeable in the NMR spectrum. It was determined by NMR and IR spectroscopy that the hydrolysis products were an imide/carboxylic acid and an imide/anhydride. Model B was then aged for 1200 h at 80 °C to quantitatively determine the amount of hydrolysis products as a function of time. The relative intensity of the peaks due to carboxylic acid is constant after some time. The authors suggest that an equilibrium occurs between model B and the products formed during hydrolysis, and therefore, the conversion to hydrolysis products is limited to about 12%. This critical fraction is probably enough to cause some degradation of polymeric materials, but research on six-membered polyimides has remained active. 

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