Adsorption of surfactant molecules onto the surface of colloidal particles: Case of like-charged species

Mixed systems of nanoparticles and surfactants have a broad range of applications from consumer products and medicine to inkjet printing and oil recovery. The interparticle interactions can be tuned in presence of surfactants and are dependent on surface charge of both species, particle's wettability, surfactant solubility, and solution conditions such as electrolyte concentration and pH. The case of oppositely charged particles and surfactants has been extensively examined in the literature, primarily to tune the wettability of particles. In contrast, the behavior in systems of like-charged species such as negatively charged particles and anionic surfactants remains poorly understood, with conflicting findings reported in previous studies on the adsorption of surfactants. By conducting a comprehensive investigation, in this study we shed light on the factors that influence the adsorption of surfactant onto the particle surface, both promoting and preventing it, and unravel the underlying mechanisms governing such behavior. Silica nanoparticles were used as the negatively charged particle, sodium dodecyl sulfate (SDS) was used as the surfactant and potassium nitrate was used as the salt, while the pH was adjusted by potassium hydroxide and nitric acid, to investigate the effect of surfactants on the surface characteristics of the silica nanoparticles under various operating conditions. The zeta potential of particles along with the solution conductivity were obtained via mobility measurements. Using this information, the solution's Debye length and the particle's surface charge density were estimated. It was found that interpreting the outcome solely based on the zeta potential data might not reveal the adsorption of SDS onto the particle surface as no supercharging effect could be detected in some cases. However, shifting the perspective to charge density shows that SDS increased the particles charge density for pH values in the range of 2-5, corresponding to the pH conditions at which vicinal and geminal silanol groups are dissociated. This effect was more pronounced at moderate total ionic strengths between 1 and 10 mM, where SDS activity was found to be higher and the Debye length was sufficiently short. The increase in the particle's charge density was attributed to the tail-down adsorption of SDS onto the particle surface via entropically-driven interactions. These findings offer valuable insights into like-charged mixed particle/surfactant systems and bring clarity to the scientific community regarding this complex and previously inconclusive topic.