Surface adsorption of zwitterionic surfactants: n-alkyl phosphocholines characterised by surface tensiometry and neutron reflection

Abstract

The surface adsorption of n-dodecyl phosphocholine (C 12PC) has been characterised by a combined measurement of surface tension and neutron reflectivity. The critical micellar concentration (CMC) was found to be 0.91 mM at 25 °C in pure water. At the CMC, the limiting area per molecule ( A cmc ) was found to be 52 ± 3 Å 2 and the surface tension ( γ cmc ) to be ca. 40.0 ± 0.5 mN / m . The parallel study of chain isomer n-hexadecyl phosphocholine (C 16PC) showed a decrease of the CMC to 0.012 mM and a drop of γ cmc to 38.1 ± 0.5 mN / m . However, A cmc for C 16PC was found to be 54 ± 3 Å 2 , showing that increase in alkyl chain length by four methylene groups has little effect on A cmc . The almost constant A cmc suggested that the limiting area per molecule was determined by the bulky PC head group. It was further found that the surface tension and related key physical parameters did not vary much with temperature, salt addition, solution pH or any combination of these, thus showing that surface adsorption and solution aggregation from PC surfactants is largely similar to the zwitterionic betaine surfactants and is distinctly different from ionic and non-ionic surfactants. The thickness of the adsorbed monolayers measured from both dC 12hPC and dC 16hPC was found to be 20–22 Å at the CMC from neutron reflectivity. Neither A cmc nor layer thickness varied with alkyl chain length, indicating that as the alkyl chain length became longer it was further tilted away from the surface normal direction and the layer packing density increased. It was also observed that the thickness of the layer varied little with surfactant concentration, indicating that the average conformational orientation of the alkyl chain remained unchanged against varying surface coverage.