Effect of the Addition of a Cross-Linker and the Water pH on the Physical Properties of Films of pH-Responsive Polymer Particles at Air/Water Interfaces.

We investigated how the stiffness and physical properties of films of pH-responsive polystyrene nanoparticles with poly(2-(N,N-dimethylamino)ethylmethacrylate) hairs (PDMA-PS particles) at air/water interfaces could be varied by using the cross-linker of 1,2-bis-(2-iodoethoxy)ethane (BIEE) and by varying the water pH. The physical properties of the film were investigated by using a Langmuir trough, atomic force microscope, and monolayer particle interaction apparatus. Films without large (μm-sized) holes were prepared by reacting BIEE with the PDMA-PS particles in the ethanol spreading solution for times ≤6 h and then by spreading this solution on a pH 5.8 water surface. Longer reaction times or a pH 9.0 water surface gave films with large holes. The holes were the result of the presence of aggregates of various sizes, which could not efficiently pack in the film. The aggregates were formed by interparticle adhesions because of the BIEE presence and physical attractive forces. The pH 5.8 water gave less aggregation than the pH 9.0 water because of the stronger interparticle electrostatic repulsions that resulted from the higher particle charge in pH 5.8 water than pH 9.0 water. The holes in the films could be decreased by reacting BIEE with the PDMA-PS particles on the pH 5.8 or 9.0 water surface, while the film was compressed to give a close packing density. The stiffness of the film of PDMA-PS particles increased, when BIEE was reacted with the PDMA-PS particles in the spreading solution for 1 h and was then spread on a pH 5.8 water surface. The film stiffness, however, did not increase, when BIEE was reacted with PDMA-PS particles on the pH 5.8 or 9.0 water surface for 1 h. This stiffness difference was explained by the fact that the former method gave a thicker film than the latter method.