Dc. Duffy et al., POLYMER-SURFACTANT AGGREGATES AT A HYDROPHOBIC SURFACE STUDIED USING SUM-FREQUENCY VIBRATIONAL SPECTROSCOPY, Langmuir, 11(8), 1995, pp. 2931-2937
The structure of polymer-surfactant aggregates adsorbed at a hydrophob
ic surface has been investigated using sum-frequency spectroscopy (SFS
). The surface vibrational spectra of a cationic surfactant (tetradecy
ltrimethylammonium bromide) show that the surfactant molecules form an
oriented monolayer at the surface, with the polymer electrostatically
binding to the charged head groups of the surfactant at the interface
with the aqueous phase. The polymer-surfactant interaction, however,
does not appear to increase the maximum packing density of the surfact
ant layer above that of a monolayer of pure surfactant at its cmc. The
general structural features of the surfactant layer remain unaffected
by the presence of polymer, but steric and hydrophobic interactions b
etween the polymer and surfactant influence the detailed adsorbate str
ucture. The sum-frequency spectra indicate that low concentrations of
negatively charged polymers cause the adsorption of surfactant at lowe
r concentrations than from a solution of pure surfactant. The effects
of pH, polymer concentration, and added electrolyte on the polymer-sur
factant adsorbate have been examined. The SF spectrum of the poly(acry
lic acid) and deuterated cationic surfactant adsorbate provides eviden
ce that this polymer also adopts a preferential orientation at the sur
face under certain conditions.