Corrosion of conducting polymers in aqueous electrolytes

Abstract The corrosion of polythiophene, poly-bisthiophene and poly-3-methylthiophene in aqueous electrolytes at pH 1 to 13 was investigated. Corrosion rate was determined experimentally by potentiodynamic discharge of residual redox capacity of the conducting polymer after exposure to the corrosion medium. Two corrosion reactions were found to proceed after quasi first order kinetics. The initial rapid process is due to an electrochemical mechanism. The cathodic undoping is balanced by an anodic overoxidation reaction, even at the relatively negative potentials. A rather slow second process is caused by chemical attack of nucleophiles dissolved in the solid at the remaining radical cationic centers. Both rate constants are appreciably larger than those measured previously for polypyrrole, and they increase with increasing pH. The acceleration is due to the more positive redox potentials for polythiophenes. From the exponenetial decay of the corrosion potential with time, the same rate constants could be evaluated. In contrast to polypyrrole, the polymer backbone conjugation is not interrupted initially due to - S - → - SO 2 - , and recharge is possible to some extent.