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Polystyrenesulfonate acid (PSS) and alkyltrimethylammonium bromide (C nTAB, n= 8, 14, or 18) were dissolved in a chloroform/methanol solution and cospread on an air/water interface. The surfactant−polyelectrolyte interaction leads to the formation of hydrophobic complexes which are able to spread well at the air/water interface. The effects of surfactant chain length and surfactant/polymer ratio on the characteristics of the mixed monolayers were studied in terms of surface pressure−area (π− A) isotherm, area relaxation, and hysteresis behavior as well as the surface morphology and composition of the corresponding Langmuir−Blodgett films. The mixed monolayers prepared by cospreading method are also compared with the complex monolayers prepared by preprecipitation of the surfactant−polyelectrolyte complexes from an aqueous solution. The experimental results show that the chain length of an incorporated surfactant is the main factor determining the properties of a complex monolayer. By using a longer chain surfactant to complex with polyelectrolyte, a more condensed monolayer with higher collapse pressure and stability can be obtained. For the effect of surfactant/polymer ratio (S/P), it is found that an increase of S/P ratio not only produces more complexes capable of staying at the air/water interface but also affects the incorporation of uncomplexed surfactant into the mixed monolayer. The X-ray photoelectron spectroscopy (XPS) analysis shows that the amount of uncomplexed surfactant is higher at low S/P value (0.2) and is insignificant when the S/P value increases to about 1.0 or 2.0, where a maximum amount of complexes were formed at the interface. A further increase of S/P ratio may cause additional incorporation of uncomplexed surfactant and/or micellization of surfactant around PSS cores, depending on the surfactant chain length. A model illustrating the incorporation and spreading of the surfactant−polyelectrolyte complexes at the air/water interface was proposed. [ABSTRACT FROM AUTHOR]

Gold nanoparticles (Au NPs) were prepared and surface-modified by mercaptosuccinic acid (MSA) to render a surface with carboxylic acid groups (MSA-Au). Octadecylamine (ODA) was used as a template monolayer to adsorb the Au NPs dispersed in the subphase. The effect of MSA concentration on the incorporation of Au NPs on the ODA monolayer and the relevant behavior of the mixed monolayer were studied using the pressure−area (−A) isotherm and transmission electron microscopy (TEM) observations. The experimental results showed that the adsorbed density of Au NPs is low without the surface modification by MSA. When MSA was added into the Au NP-containing subphase, the incorporation amount of Au NPs increased with increasing MSA concentration up to ∼1 × 10-5M for the particle density of 1.3 × 1011particles/mL. With a further increase in the MSA concentration, the adsorbed particle density decreases due to competitive adsorption between the free MSA molecules and the MSA-Au NPs. It is inferred that free MSA molecules adsorb more easily than the MSA-Au NPs on the ODA monolayer. Therefore, an excess amount of MSA present in the subphase is detrimental to the incorporation of gold particles. The study on the monolayer behavior also shows that the −Aisotherm of the ODA monolayer shifts right when small amounts of Au NPs or free MSA molecules are incorporated. However, when larger amounts of particles are adsorbed at the air/liquid interface, a left shift of the −Aisotherm appears, probably due to the adsorption of ODA molecules onto the particle surface and the transferring of the particles from beneath the ODA monolayer to the air/water interface. According to the present method, it is possible to prepare uniform particulate films of controlled densities by controlling the particle concentration in the subphase, the MSA concentration, and the surface pressure of a mixed monolayer. [ABSTRACT FROM AUTHOR]