Viscoelastic phenomena during electrochemical deposition of polyaniline films

Electrochemical quartz crystal microbalance (EQCM) and crystal admittance measurements were used to study the potentiodynamic electrodeposition of polyaniline films. Variations in peak admittance provided the distinction between acoustically thin and acoustically thick films. In the former instance, the Sauerbrey equation was used to interpret the EQCM frequency shift in gravimetric terms. In the latter case, admittance spectra were interpreted viscoelastically to yield shear storage and loss moduli. Variations in storage modulus with potential (within a given deposition cycle) and with number of deposition cycles (at a given potential) were small, covering the range 1.1–1.6 × 10⁷ dyn cm⁻². Variations in loss modulus were much more dramatic, increasing from very low levels typical of a simple fluid to values similar to the storage modulus. More subtle variations of both components within a single potential cycle were highlighted using a novel differential format. This revealed two peaks, correlating with the first film redox process and with further film oxidation/polymerization. Contribution to the International Workshop on Electrochemistry of Electroactive Materials (WEEM-2006), Repino, Russia, 24–29 June 2006.