Mechanism of actuation in conducting polymers: Osmotic expansion

Conducting polymers expand or contract when their redox state is changed. This expansion/contraction effect can be separated in an intrinsic part because of changes of the polymer backbone on reduction/oxidation and a part depending on the surrounding electrolyte phase, because of osmotic expansion of the polymer phase. The osmotic effect causes solvent molecules to move into the polymer in a number far in excess of those bound strongly in the solvation shell of the mobile ion, resulting in large volume changes. In this paper, a thermodynamic description of the osmotic expansion is worked out. The model is compared with measurements on PPy(DBS) films. The experiments show that the expansion decreases as the electrolyte concentration is increased. This means that a considerable part of the total expansion is due to the osmotic effect. The osmotic effect should be taken into account when interpreting and designing actuator experiments and when comparing experimental results from different sources.