States of adsorbed dodecyl amine and water at a silica surface as revealed by vibrational spectroscopy.

States of adsorbed dodecylamine (DDA) at a silica surface have been studied as a function of pH by vibrational spectroscopy (SFVS, FTIR), contact angle measurements, and molecular dynamics (MD) simulations. The results show that the state of adsorbed DDA at a silica surface varies significantly at different pH values. At pH 6.30, there is no pronounced adsorption of DDA cations and the surface is hydrophilic. At pH 10.0, the vibrational spectroscopy results together with contact angle measurements and MD simulations suggest that amine is adsorbed as a well organized monolayer, the hemimicelle structure. Under these conditions, dehydration occurs based on SFVS analysis and the silica surface becomes hydrophobic. In the case of pH 12.3, it has been confirmed that continued adsorption of DDA neutral molecules occurs with the amine surface state changing from a monolayer to a bilayer or a micellar surface state as revealed both from SFVS analysis and MD simulations. At this high pH, extensive surface hydration is evident from SFVS results and the silica surface becomes hydrophilic.