Tuning the Structure and Rheology of Polystyrene Particles at the Air-Water Interface by Varying the pH

We form films of carboxylated polystyrene particles (C-PS) at the air-water interface and investigate the effect of subphase pH on their structure and rheology by using a suite of complementary experimental techniques. Our results suggest that electrostatic interactions drive the stability and the structural order of the films. In particular, we show that by increasing the pH of the subphase from 9 up to 13, the films exhibit a gradual transition from solid to liquidlike, which is accompanied by a loss of the long-range order (that characterizes them at lower values of pH). Direct optical visualization of the layers, scanning electron microscopy, and surface pressure isotherms indicate that the particles deposited at the interface form three-dimensional structures involving clusters, with the latter being suppressed and a quasi-2D particle configuration eventually reached at the highest pH values. Evidently, the properties of colloidal films can be tailored significantly by altering the pH of the subphase.