The surface excess of sodium dodecyl sulfate (SDS) in aqueous solutions of SDS and the polymer poly(vinylpyrrolidone) (PVP) has been measured as a function of SDS and PVP concentrations using neutron reflection. Below the critical aggregation concentration (CAC) the adsorption of SDS is increased by the presence of PVP, indicating that the two components interact cooperatively at the surface. Between the CAC and the critical micelle concentration (CMC) of the surfactant there is a slight depletion of SDS from the surface. Comparison of coverages determined by neutron reflection with those from earlier radiotracer work indicates that, in the higher concentration range, PVP is bound to the surfactant layer, creating a region from which surfactant is depleted, which is further evidence for a strong polymer/surfactant interaction at the surface. Comparison of the effect of added PVP on the surface tension with the neutron reflection measurements indicates that, even below the CAC, the surfactant complexes to the polymer to some extent in the bulk solution. There are no measurable effects of the polymer on the thickness of the surfactant layer at any concentration. There is an indication that at the surface the surfactant is slightly displaced outward from water on addition of polymer, but accurate structural determination of the mixed layer proved too difficult to be certain of this result.

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