Interactions between Colloidal Particles in the Presence of an Ultrahighly Charged Amphiphilic Polyelectrolyte

A novel amphiphilic polyelectrolyte denoted as PAGC(8) and a traditional amphiphilic polyelectrolyte denoted as PASC(8) were prepared. PAGC8 consisted of gemini-type surfactant segment based on 1,3-bis (N,N-dimethyl-N-octylammonium)-2-propyl acrylate dibromide, while PASC(8) incorporated acryloyloxyethyl-N,N-dimethyl-N-dodecylammonium bromide as single chain surfactant units within its repeat unit structure. Turbidity, stability, and zeta potential measurements were performed in the presence of PAGC(8) and PASC(8), respectively, to evaluate their effectiveness in inducing solid/liquid separations. It was found that the maximum transmittance was observed before the zeta potential values reached the isoelectric point, implying that not only charge neutralization but also charge-patch mechanism contributed to the separation process. Colloid probe atomic force microscopy technique was introduced to directly determine the interactions between surfaces in the presence of ultrahighly charged amphiphilic polyelectrolyte. On the basis of the AFM results, we have successfully interpreted the influence of the charge density of the polyelectrolytes on the phase stability. Electrostatic interaction played the dominant role in the flocculation processes, although both electrostatic interaction and hydrophobic effect provided contributions to the colloidal dispersions. The attractions upon surfaces approach in the case of PAGC(8) were significantly larger than that of PASC(8) due to the higher charge density. The strong peeling events upon retraction in the presence of PAGC(8) implied that the hydrophobic effect was stronger than that of PASC(8), which displayed the loose pulling events. A strong attraction was identified at shorter separation distances for both systems. However, these interactions cannot be successfully described by the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory of colloid stability due to the participation of charge-patch and strong hydrophobic effect. To account for the additional interactions, we proposed an extended DLVO empirical model to explain the non-DLVO forces in the systems. A reasonable physical model was also proposed to further describe the interactions between surfaces in the two amphiphilic polyelectrolyte systems.