Interrelations between charging, structure and electrokinetics of nanometric polyelectrolyte films.

Streaming current, surface conductivity and swelling data of poly(acrylic acid) (PAA) and poly(ethylene imine) (PEI) thin films are analyzed on the basis of the theory for diffuse soft interfaces (J.F.L. Duval, R. Zimmermann, A. L. Cordeiro, N. Rein, C. Werner, Langmuir 25 (2009) 10691). Focus is put on ways to unravel the electroosmotic and migration contributions of the measured surface conductivity, which is crucial for appropriate electrokinetic analysis of films carrying high densities of dissociable groups. Results demonstrate that the osmotically-driven swelling of the PAA films with increasing pH is accompanied by an increase in diffuseness for the interphasial polymer segment density distribution. This heterogeneity is particularly marked at low ionic strength with a non-monotonous dependence of the streaming current on pH and the presence of a maximum at pH∼6.5. The analysis of the PEI films evidences heterogeneous swelling with lowering pH, i.e. upon protonation of the amine groups. The characteristic decay length in the interphasial PEI segment density distribution is found to be nearly independent of the pH, which is in line with the moderate swelling determined by ellipsometry. A critical discussion is given on the strengths and limitations of electrokinetics/surface conductivity for quantifying the coupled electrohydrodynamic and structural properties of moderately to highly swollen polyelectrolyte thin films.