Compression and structure of monolayers of charged latex particles at air/water and octane/water interfaces

We have studied the compression and structure of compressed monolayers of sulfate polystyrene latex particles on air/water and octane/water interfaces. If compressed sufficiently (on a Langmuir trough) the monolayers at air/water surfaces give rafts of hexagonally packed particles, while those at oil/water interfaces undergo a transition from the originally hexagonal to a rhombohedral structure. We have found that beyond collapse the particle monolayers on both air/water and octane/water interfaces fold and corrugate, and there is no expulsion of individual particles or particle aggregates from the interface. In the case of air/water interfaces, the structuring of particle monolayers (below collapse) was found to be very sensitive to the electrolyte concentration in the aqueous phase. At low electrolyte concentration, a fairly ordered structure resulting from the interparticle repulsion was observed, while at high electrolyte concentration, the particles form 2D clusters. In marked contrast, particle monolayers at octane/water interfaces remain highly ordered as a result of long-range repulsion, even on concentrated electrolyte solution. We attribute the enhanced lateral repulsion between the latex particles at the octane/water interface to the existence of residual surface charges at the particle/octane interface. We propose a simple model, which describes the electrostatic interaction between the adsorbed particles and includes the effect of image forces. From this we have derived an analytic formula for the electrostatic surface pressure vs trough area, which agrees well with the experimental data over a wide range of surface pressure.