Effects of degassing and ionic strength on AFM force measurements in octadecyltrimethylammonium chloride solutions

Sakamoto et al. (Langmuir 2002, 18, 5713) conducted AFM force measurements between silica sphere and fused-silica plate in aqueous octadecyltrimethylammonium chloride (C ₁₆TACl) solutions and concluded that long-range attractive force is not observed in carefully degassed solutions. In the present work, AFM force measurements were conducted by following the procedures described by Sakamoto et al. The results showed the presence of an attractive force that was much stronger than the van der Waals force both in air-saturated and degassed solutions. The force was most attractive at 5 × 10 ^-6 M C ₁₈TACl, where contact angle was maximum. At this concentration, which is close to the charge compensation point (ccp) of the glass sphere, the long-range decay lengths (D) were 34 and 38 nm in air-saturated and degassed solutions, respectively. At 10 ^-5 M, the decay length decreased from 30 to 4 nm upon degassing. This decrease in decay length can be explained by a pH increase (from 5.7 to 6.6), which in turn causes additional surfactant molecules to adsorb on the surface with inverse orientation. The attractive force was screened by an added electrolyte (NaCl), indicating that the attractive force may be of electrostatic origin. Therefore, the very long decay lengths observed in the absence of electrolyte may be ascribed to the fact that the ccp occurs at a very low surfactant concentration.