Characterisation of phase transition in adsorbed monolayers at the air/water interface

Abstract

Recent work has provided experimental and theoretical evidence that a first order fluid/condensed (LE/LC) phase transition can occur in adsorbed monolayers of amphiphiles and surfactants which are dissolved in aqueous solution. Similar to Langmuir monolayers, also in the case of adsorbed monolayers, the existence of a G/LE phase transition, as assumed by several authors, is a matter of question. Representative studies, at first performed with a tailored amphiphile and later with numerous other amphiphiles, also with n-dodecanol, provide insight into the main characteristics of the adsorbed monolayer during the adsorption kinetics. The general conditions necessary for the formation of a two-phase coexistence in adsorbed monolayers can be optimally studied using dynamic surface pressure measurements, Brewster angle microscopy (BAM) and synchrotron X-ray diffraction at grazing incidence (GIXD). A characteristic break point in the time dependence of the adsorption kinetics curves indicates the phase transition which is largely affected by the concentration of the amphiphile in the aqueous solution and on the temperature. Formation and growth of condensed phase domains after the phase transition point are visualised by BAM. As demonstrated by a tailored amphiphile, various types of morphological textures of the condensed phase can occur in different temperature regions. Lattice structure and tilt angle of the alkyl chains in the condensed phase of the adsorbed monolayer are determined using GIXD. The main growth directions of the condensed phase textures are correlated with the two-dimensional lattice structure. The results, obtained for the characteristics of the condensed phase after a first order main transition, are supported by experimental bridging to the Langmuir monolayers. Phase transition of adsorbing trace impurities in model surfactants can strongly affect the characteristics of the main component. Dodecanol present as minor component in aqueous sodium dodecylsulfate solution dominate largely the fundamental features of the adsorbed monolayer of the mixed dodecanol/SDS solutions at adsorption equilibrium. A theoretical concept on the basis of the quasi-chemical model and assumption of the entropy non-ideality has been developed which can well describe the experimental results of the diffusion kinetics of surfactant adsorption from solutions. The model regards the phase behaviour of adsorbed monolayers on the basis of the experimental results explicitly supported by the first order fluid/condensed phase transition and theoretical models assuming bimodal distribution between large aggregates (domains) and monomers and/or very small aggregates. Another simple theoretical model for the description of the coadsorption of surfactant mixtures, based on the additivity of the contributions brought by the solution components into the surface pressure is shown to be in qualitative agreement with the experimental data of mixed dodecanol/SDS solutions. The theoretical results corroborate the fact that the formed condensed phase (large aggregates) in the mixed monolayer consists mainly of dodecanol.