Dynamic Surface Tension of Aqueous Solutions of Ionic Surfactants: Role of Electrostatics

The adsorption kinetics of the cationic surfactant dodecyltrimethylammonium bromide at the air-water interface has been studied by the maximum bubble pressure method at concentrations below the critical micellar concentration. At short times, the adsorption is diffusion-limited. At longer times, the surface tension shows an intermediate plateau and can no longer be accounted for by a diffusion limited process. Instead, adsorption appears kinetically controlled and slowed down by an adsorption barrier. A Poisson-Boltzmann theory for the electrostatic repulsion from the surface does not fully account for the observed potential barrier. The possibility of a surface phase transition is expected from the fitted isotherms but has not been observed by Brewster angle microscopy.Comment: 13 pages, 5 figure

Contribution of Cross-Correlations to the 21cm Angular Power Spectrum in the Epoch of Reionization

Measurement of the 21cm hyperfine transition of neutral hydrogen provides a unique probe of the epoch of reionization and the Dark Ages. Three major mechanisms are believed to dominate the radiation process: emission from neutral hydrogen surrounding the ionized bubbles of first galaxies and/or quasars, emission from neutral hydrogen inside minihalos, and absorption of diffuse neutral hydrogen against the cosmic microwave background. In the present work, by simply combining the existing analytic models for the three mechanisms, we investigate the contribution of cross-correlation between these three components to the total 21cm angular power spectrum, in the sense that neutral hydrogen associated with different radiation processes traces the large-scale structures of underlying density perturbations. While the overall 21cm power spectrum remains almost unchanged with the inclusion of the cross-correlations, the cross-correlation may play a key role in the determination of the 21cm power spectrum during the transition of 21cm radiation from emission-dominated phase to absorption-dominated phase at redshift z~20. A significant suppression in the 21cm angular power spectrum during this transition is anticipated as the result of negative contribution of the cross-correlation between the absorption of diffuse neutral hydrogen and the emission components. Therefore, an accurate prediction of the cosmic 21cm power spectrum should take the cross-correlation into account especially at the transition phase.Comment: 10 pages, 4 figures, accepted for publication in MNRA

Self-Assembly in Mixtures of Polymers and Small Associating Molecules

The interaction between a flexible polymer in good solvent and smaller associating solute molecules such as amphiphiles (surfactants) is considered theoretically. Attractive correlations, induced in the polymer because of the interaction, compete with intra-chain repulsion and eventually drive a joint self-assembly of the two species, accompanied by partial collapse of the chain. Results of the analysis are found to be in good agreement with experiments on the onset of self-assembly in diverse polymer-surfactant systems. The threshold concentration for self-assembly in the mixed system (critical aggregation concentration, cac) is always lower than the one in the polymer-free solution (critical micelle concentration, cmc). Several self-assembly regimes are distinguished, depending on the effective interaction between the two species. For strong interaction, corresponding experimentally to oppositely charged species, the cac is much lower than the cmc. It increases with ionic strength and depends only weakly on polymer charge. For weak interaction, the cac is lower but comparable to the cmc, and the two are roughly proportional over a wide range of cmc values. Association of small molecules with amphiphilic polymers exhibiting intra-chain aggregation (polysoaps) is gradual, having no sharp onset.Comment: 21 pages, 5 figures, RevTex, the published version, see also cond-mat/990305